Search results for: bound entanglement

Authors: Esther Van Andel, Stefanie C. Lange, Maarten M. J. Smulders, Han Zuilhof

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False outcomes of diagnostic tests are a major concern in medical health care. To improve the reliability of surface-based diagnostic tests, it is of crucial importance to diminish background signals that arise from the non-specific binding of biomolecules, a process called fouling. The aim is to create surfaces that repel all biomolecules except the molecule of interest. This can be achieved by incorporating antifouling protein repellent coatings in between the sensor surface and it’s recognition elements (e.g. antibodies, sugars, aptamers). Zwitterionic polymer brushes are considered excellent antifouling materials, however, to be able to bind the molecule of interest, the polymer brushes have to be functionalized and so far this was only achieved at the expense of either antifouling or binding capacity. To overcome this limitation, we combined both features into one single monomer: a zwitterionic sulfobetaine, ensuring antifouling capabilities, equipped with a clickable azide moiety which allows for further functionalization. By copolymerizing this monomer together with a standard sulfobetaine, the number of azides (and with that the number of recognition elements) can be tuned depending on the application. First, the clickable azido-monomer was synthesized and characterized, followed by copolymerizing this monomer to yield functionalizable antifouling brushes. The brushes were fully characterized using surface characterization techniques like XPS, contact angle measurements, G-ATR-FTIR and XRR. As a proof of principle, the brushes were subsequently functionalized with biotin via strain-promoted alkyne azide click reactions, which yielded a fully zwitterionic biotin-containing 3D-functionalized coating. The sensing capacity was evaluated by reflectometry using avidin and fibrinogen containing protein solutions. The surfaces showed excellent antifouling properties as illustrated by the complete absence of non-specific fibrinogen binding, while at the same time clear responses were seen for the specific binding of avidin. A great increase in signal-to-noise ratio was observed, even when the amount of functional groups was lowered to 1%, compared to traditional modification of sulfobetaine brushes that rely on a 2D-approach in which only the top-layer can be functionalized. This study was performed on stoichiometric silicon nitride surfaces for future microring resonator based assays, however, this methodology can be transferred to other biosensor platforms which are currently being investigated. The approach presented herein enables a highly efficient strategy for selective binding with retained antifouling properties for improved signal-to-noise ratios in binding assays. The number of recognition units can be adjusted to a specific need, e.g. depending on the size of the analyte to be bound, widening the scope of these functionalizable surface coatings.

Keywords: antifouling, signal-to-noise ratio, surface functionalization, zwitterionic polymer brushes

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Authors: Milu T. Cherian, Sergio C. Chai, Morgan A. Casal, Taosheng Chen

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This study aims to use CINPA1, a recently discovered small-molecule inhibitor of the xenobiotic receptor CAR (constitutive androstane receptor) for understanding the binding modes of CAR and to guide CAR-mediated gene expression profiling studies in human primary hepatocytes. CAR and PXR are xenobiotic sensors that respond to drugs and endobiotics by modulating the expression of metabolic genes that enhance detoxification and elimination. Elevated levels of drug metabolizing enzymes and efflux transporters resulting from CAR activation promote the elimination of chemotherapeutic agents leading to reduced therapeutic effectiveness. Multidrug resistance in tumors after chemotherapy could be associated with errant CAR activity, as shown in the case of neuroblastoma. CAR inhibitors used in combination with existing chemotherapeutics could be utilized to attenuate multidrug resistance and resensitize chemo-resistant cancer cells. CAR and PXR have many overlapping modulating ligands as well as many overlapping target genes which confounded attempts to understand and regulate receptor-specific activity. Through a directed screening approach we previously identified a new CAR inhibitor, CINPA1, which is novel in its ability to inhibit CAR function without activating PXR. The cellular mechanisms by which CINPA1 inhibits CAR function were also extensively examined along with its pharmacokinetic properties. CINPA1 binding was shown to change CAR-coregulator interactions as well as modify CAR recruitment at DNA response elements of regulated genes. CINPA1 was shown to be broken down in the liver to form two, mostly inactive, metabolites. The structure-activity differences of CINPA1 and its metabolites were used to guide computational modeling using the CAR-LBD structure. To rationalize how ligand binding may lead to different CAR pharmacology, an analysis of the docked poses of human CAR bound to CITCO (a CAR activator) vs. CINPA1 or the metabolites was conducted. From our modeling, strong hydrogen bonding of CINPA1 with N165 and H203 in the CAR-LBD was predicted. These residues were validated to be important for CINPA1 binding using single amino-acid CAR mutants in a CAR-mediated functional reporter assay. Also predicted were residues making key hydrophobic interactions with CINPA1 but not the inactive metabolites. Some of these hydrophobic amino acids were also identified and additionally, the differential coregulator interactions of these mutants were determined in mammalian two-hybrid systems. CINPA1 represents an excellent starting point for future optimization into highly relevant probe molecules to study the function of the CAR receptor in normal- and pathophysiology, and possible development of therapeutics (for e.g. use for resensitizing chemoresistant neuroblastoma cells).

Keywords: antagonist, chemoresistance, constitutive androstane receptor (CAR), multi-drug resistance, structure activity relationship (SAR), xenobiotic resistance

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Authors: Venus Torabi

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ISIS, the terrorist organization, modified two videogames, ARMA III and Grand Theft Auto 5 (2013) as means of online recruitment and ideological propaganda. The urge to study the mechanism at work, whether it has been successful or not, derives (Digital) Humanities experts to explore how codes of terror, Islamic ideology and recruitment strategies are incorporated into the ludic mechanics of videogames. Another aspect of the significance lies in the fact that this is a latent problem that has not been fully addressed in an interdisciplinary framework prior to this study, to the best of the researcher’s knowledge. Therefore, due to the complexity of the subject, the present paper entangles with game studies, philosophical and religious poles to form the methodology of conducting the research. As a contextualized epistemology of such exploitation of videogames, the core argument is building on the notion of “Culture Industry” proposed by Theodore W. Adorno and Max Horkheimer in Dialectic of Enlightenment (2002). This article posits that the ideological underpinnings of ISIS’s cause corroborated by the action-bound mechanics of the videogames are in line with adhering to the Islamic Eschatology as a furnishing ground and an excuse in exercising terrorism. It is an account of ISIS’s modification of the videogames, a tool of technological progression to practice online radicalization. Dialectically, this practice is packed up in rhetoric for recognizing a religious myth (the advent of a savior), as a hallmark of regression. The study puts forth that ISIS’s wreaking havoc on the world, both in reality and within action videogames, is negotiating the process of self-assertion in the players of such videogames (by assuming one’s self a member of terrorists) that leads to self-annihilation. It tries to unfold how ludic Mod videogames are misused as tools of mass deception towards ethnic cleansing in reality and line with the distorted Eschatological myth. To conclude, this study posits videogames to be a new avenue of mass deception in the framework of the Culture Industry. Yet, this emerges as a two-edged sword of mass deception in ISIS’s modification of videogames. It shows that ISIS is not only trying to hijack the minds through online/ludic recruitment, it potentially deceives the Muslim communities or those prone to radicalization into believing that it's terrorist practices are preparing the world for the advent of a religious savior based on Islamic Eschatology. This is to claim that the harsh actions of the videogames are potentially breeding minds by seeds of terrorist propaganda and numbing them to violence. The real world becomes an extension of that harsh virtual environment in a ludic/actual continuum, the extension that is contributing to the mass deception mechanism of the terrorists, in a clandestine trend.

Keywords: culture industry, dialectic, ISIS, islamic eschatology, mass deception, video games

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Authors: Marcel Schulze, Behrem Aslan, Silke Lux, Alexandra Philipsen

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Objective: Patients with Attention Deficit/Hyperactivity Disorder (ADHD) often report that they are being flooded by sensory impressions. Studies investigating sensory processing show hypersensitivity for sensory inputs across the senses in children and adults with ADHD. Especially the auditory modality is affected by deficient acoustical inhibition and modulation of signals. While studying unimodal signal-processing is relevant and well-suited in a controlled laboratory environment, everyday life situations occur multimodal. A complex interplay of the senses is necessary to form a unified percept. In order to achieve this, the unimodal sensory modalities are bound together in a process called multisensory integration (MI). In the current study we investigate MI in an adult ADHD sample using the McGurk-effect – a well-known illusion where incongruent speech like phonemes lead in case of successful integration to a new perceived phoneme via late top-down attentional allocation . In ADHD neuronal dysregulation at rest e.g., aberrant within or between network functional connectivity may also account for difficulties in integrating across the senses. Therefore, the current study includes resting-state functional connectivity to investigate a possible relation of deficient network connectivity and the ability of stimulus integration. Method: Twenty-five ADHD patients (6 females, age: 30.08 (SD:9,3) years) and twenty-four healthy controls (9 females; age: 26.88 (SD: 6.3) years) were recruited. MI was examined using the McGurk effect, where - in case of successful MI - incongruent speech-like phonemes between visual and auditory modality are leading to a perception of a new phoneme. Mann-Whitney-U test was applied to assess statistical differences between groups. Echo-planar imaging-resting-state functional MRI was acquired on a 3.0 Tesla Siemens Magnetom MR scanner. A seed-to-voxel analysis was realized using the CONN toolbox. Results: Susceptibility to McGurk was significantly lowered for ADHD patients (ADHDMdn:5.83%, ControlsMdn:44.2%, U= 160.5, p=0.022, r=-0.34). When ADHD patients integrated phonemes, reaction times were significantly longer (ADHDMdn:1260ms, ControlsMdn:582ms, U=41.0, p<.000, r= -0.56). In functional connectivity medio temporal gyrus (seed) was negatively associated with primary auditory cortex, inferior frontal gyrus, precentral gyrus, and fusiform gyrus. Conclusion: MI seems to be deficient for ADHD patients for stimuli that need top-down attentional allocation. This finding is supported by stronger functional connectivity from unimodal sensory areas to polymodal, MI convergence zones for complex stimuli in ADHD patients.

Keywords: attention-deficit hyperactivity disorder, audiovisual integration, McGurk-effect, resting-state functional connectivity

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Authors: I. Derek Kaka’an, P. Smolianov, D. Koh Choon Lian, S. Dion, C. Schoen, J. Norberg

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This study was designed to examine mass participation and elite football performance in Nigeria with reference to advance international football management practices. Over 200 sources of literature on sport delivery systems were analyzed to construct a globally applicable model of elite football integrated with mass participation, comprising of the following three levels: macro- (socio-economic, cultural, legislative, and organizational), meso- (infrastructures, personnel, and services enabling sport programs) and micro-level (operations, processes, and methodologies for development of individual athletes). The model has received scholarly validation and showed to be a framework for program analysis that is not culturally bound. The Smolianov and Zakus model has been employed for further understanding of sport systems such as US soccer, US Rugby, swimming, tennis, and volleyball as well as Russian and Dutch swimming. A questionnaire was developed using the above-mentioned model. Survey questions were validated by 12 experts including academicians, executives from sport governing bodies, football coaches, and administrators. To identify best practices and determine areas for improvement of football in Nigeria, 120 coaches completed the questionnaire. Useful exemplars and possible improvements were further identified through semi-structured discussions with 10 Nigerian football administrators and experts. Finally, content analysis of Nigeria Football Federation’s website and organizational documentation was conducted. This paper focuses on the meso-level of Nigerian football delivery, particularly infrastructures, personnel, and services enabling sport programs. This includes training centers, competition systems, and intellectual services. Results identified remarkable achievements coupled with great potential to further develop football in different types of public and private organizations in Nigeria. These include: assimilating football competitions with other cultural and educational activities, providing favorable conditions for employees of all possible organizations to partake and help in managing football programs and events, providing football coaching integrated with counseling for prevention of antisocial conduct, and improving cooperation between football programs and organizations for peace-making and advancement of international relations, tourism, and socio-economic development. Accurate reporting of the sports programs from the media should be encouraged through staff training for better awareness of various events. The systematic integration of these meso-level practices into the balanced development of mass and high-performance football will contribute to international sport success as well as national health, education, and social harmony.

Keywords: football, high performance, mass participation, Nigeria, sport development

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Authors: Felice Elefant, Akanksha Bhatnaghar, Keegan Krick, Elizabeth Heller

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Context: The severity of Alzheimer’s Disease (AD) progression involves an interplay of genetics, age, and environmental factors orchestrated by histone acetyltransferase (HAT) mediated neuroepigenetic mechanisms. While disruption of Tip60 HAT action in neural gene control is implicated in AD, alternative mechanisms underlying Tip60 function remain unexplored. Altered RNA splicing has recently been highlighted as a widespread hallmark in the AD transcriptome that is implicated in the disease. Research Aim: The aim of this study was to identify a novel RNA binding/splicing function for Tip60 in human hippocampus and impaired in brains from AD fly models and AD patients. Methodology/Analysis: The authors used RNA immunoprecipitation using RNA isolated from 200 pooled wild type Drosophila brains for each of the 3 biological replicates. To identify Tip60’s RNA targets, they performed genome sequencing (DNB-SequencingTM technology, BGI genomics) on 3 replicates for Input RNA and RNA IPs by Tip60. Findings: The authors' transcriptomic analysis of RNA bound to Tip60 by Tip60-RNA immunoprecipitation (RIP) revealed Tip60 RNA targets enriched for critical neuronal processes implicated in AD. Remarkably, 79% of Tip60’s RNA targets overlap with its chromatin gene targets, supporting a model by which Tip60 orchestrates bi-level transcriptional regulation at both the chromatin and RNA level, a function unprecedented for any HAT to date. Since RNA splicing occurs co-transcriptionally and splicing defects are implicated in AD, the authors investigated whether Tip60-RNA targeting modulates splicing decisions and if this function is altered in AD. Replicate multivariate analysis of transcript splicing (rMATS) analysis of RNA-Seq data sets from wild-type and AD fly brains revealed a multitude of mammalian-like AS defects. Strikingly, over half of these altered RNAs were bonafide Tip60-RNA targets enriched for in the AD-gene curated database, with some AS alterations prevented against by increasing Tip60 in fly brain. Importantly, human orthologs of several Tip60-modulated spliced genes in Drosophila are well characterized aberrantly spliced genes in human AD brains, implicating disruption of Tip60’s splicing function in AD pathogenesis. Theoretical Importance: The authors' findings support a novel RNA interaction and splicing regulatory function for Tip60 that may underlie AS impairments that hallmark AD etiology. Data Collection: The authors collected data from RNA immunoprecipitation experiments using RNA isolated from 200 pooled wild type Drosophila brains for each of the 3 biological replicates. They also performed genome sequencing (DNBSequencingTM technology, BGI genomics) on 3 replicates for Input RNA and RNA IPs by Tip60. Questions: The question addressed by this study was whether Tip60 has a novel RNA binding/splicing function in human hippocampus and whether this function is impaired in brains from AD fly models and AD patients. Conclusions: The authors' findings support a novel RNA interaction and splicing regulatory function for Tip60 that may underlie AS impairments that hallmark AD etiology.

Keywords: Alzheimer's disease, cognition, aging, neuroepigenetics

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Authors: Manuel Jose Oyson

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The Intergovernmental Panel on Climate Change (IPCC) warned in its most recent report for the entire world “to both mitigate and adapt to climate change if it is to effectively avoid harmful climate impacts.” The IPCC observed “with high confidence” a more rapid rise in total anthropogenic greenhouse gas emissions (GHG) emissions from 2000 to 2010 than in the past three decades that “were the highest in human history”, which if left unchecked will entail a continuing process of global warming and can alter the climate system. Current efforts, however, to respond to the threat of global warming, such as the United Nations Framework Convention on Climate Change and the Kyoto Protocol, have focused on states, and fail to involve Transnational Corporations (TNCs) which are responsible for a vast amount of GHG emissions. Involving TNCs in the search for solutions to climate change is consistent with an acknowledgment by contemporary international law that there is an international role for other international persons, including TNCs, and departs from the traditional “state-centric” response to climate change. Putting the focus of GHG emissions away from states recognises that the activities of TNCs “are not bound by national borders” and that the international movement of goods meets the needs of consumers worldwide. Although there is no legally-binding instrument that covers TNC activities or legal responsibilities generally, TNCs have increasingly been made legally responsible under international law for violations of human rights, exploitation of workers and environmental damage, but not for climate change damage. Imposing on TNCs a legally-binding obligation to reduce their GHG emissions or a legal liability for climate change damage is arguably formidable and unlikely in the absence a recognisable source of obligation in international law or municipal law. Instead a recourse to “soft law” and non-legally binding instruments may be a way forward for TNCs to reduce their GHG emissions and help in addressing climate change. Positive effects have been noted by various studies to voluntary approaches. TNCs have also in recent decades voluntarily committed to “soft law” international agreements. This development reflects a growing recognition among corporations in general and TNCs in particular of their corporate social responsibility (CSR). While CSR used to be the domain of “small, offbeat companies”, it has now become part of mainstream organization. The paper argues that TNCs must voluntarily commit to reducing their GHG emissions and helping address climate change as part of their CSR. One, as a serious “global commons problem”, climate change requires international cooperation from multiple actors, including TNCs. Two, TNCs are not innocent bystanders but are responsible for a large part of GHG emissions across their vast global operations. Three, TNCs have the capability to help solve the problem of climate change. Assuming arguendo that TNCs did not strongly contribute to the problem of climate change, society would have valid expectations for them to use their capabilities, knowledge-base and advanced technologies to help address the problem. It would seem unthinkable for TNCs to do nothing while the global environment fractures.

Keywords: climate change law, corporate social responsibility, greenhouse gas emissions, transnational corporations

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Authors: Ben Otange, Wolfgang Parak, Florian Schulz, Michael Alexander Rubhausen

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The feasibility of extending the usage of molecular imprinting technique in complex biomolecules is demonstrated in this research. This technique is promising in diverse applications in areas such as drug delivery, diagnosis of diseases, catalysts, and impurities detection as well as treatment of various complications. While molecularly imprinted polymers MIP remain robust in the synthesis of molecules with remarkable binding sites that have high affinities to specific molecules of interest, extending the usage to complex biomolecules remains futile. This work reports on the successful synthesis of MIP from complex proteins: BSA, Transferrin, and MUC1. We show in this research that despite the heterogeneous binding sites and higher conformational flexibility of the chosen proteins, relying on their respective epitopes and motifs rather than the whole template produces highly sensitive and selective MIPs for specific molecular binding. Introduction: Proteins are vital in most biological processes, ranging from cell structure and structural integrity to complex functions such as transport and immunity in biological systems. Unlike other imprinting templates, proteins have heterogeneous binding sites in their complex long-chain structure, which makes their imprinting to be marred by challenges. In addressing this challenge, our attention is inclined toward the targeted delivery, which will use molecular imprinting on the particle surface so that these particles may recognize overexpressed proteins on the target cells. Our goal is thus to make surfaces of nanoparticles that specifically bind to the target cells. Results and Discussions: Using epitopes of BSA and MUC1 proteins and motifs with conserved receptors of transferrin as the respective templates for MIPs, significant improvement in the MIP sensitivity to the binding of complex protein templates was noted. Through the Fluorescence Correlation Spectroscopy FCS measurements on the size of protein corona after incubation of the synthesized nanoparticles with proteins, we noted a high affinity of MIPs to the binding of their respective complex proteins. In addition, quantitative analysis of hard corona using SDS-PAGE showed that only a specific protein was strongly bound on the respective MIPs when incubated with similar concentrations of the protein mixture. Conclusion: Our findings have shown that the merits of MIPs can be extended to complex molecules of higher biomolecular mass. As such, the unique merits of the technique, including high sensitivity and selectivity, relative ease of synthesis, production of materials with higher physical robustness, and higher stability, can be extended to more templates that were previously not suitable candidates despite their abundance and usage within the body.

Keywords: molecularly imprinted polymers, specific binding, drug delivery, high biomolecular mass-templates

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Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury

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Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.

Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies

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Authors: Massimo Ferrari, Maria Sole Pagliari

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Pollution is a classic example of economic externality: agents who produce it do not face direct costs from emissions. Therefore, there are no direct economic incentives for reducing pollution. One way to address this market failure would be directly taxing emissions. However, because emissions are global, governments might as well find it optimal to wait let foreign countries to tax emissions so that they can enjoy the benefits of lower pollution without facing its direct costs. In this paper, we first document the empirical relation between pollution and economic output with static and dynamic regression methods. We show that there is a negative relation between aggregate output and the stock of pollution (measured as the stock of CO₂ emissions). This relationship is also highly non-linear, increasing at an exponential rate. In the second part of the paper, we develop and estimate a two-country, two-sector model for the US and the euro area. With this model, we aim at analyzing how the public sector should respond to higher emissions and what are the direct costs that these policies might have. In the model, there are two types of firms, brown firms (which produce a polluting technology) and green firms. Brown firms also produce an externality, CO₂ emissions, which has detrimental effects on aggregate output. As brown firms do not face direct costs from polluting, they do not have incentives to reduce emissions. Notably, emissions in our model are global: the stock of CO₂ in the economy affects all countries, independently from where it is produced. This simplified economy captures the main trade-off between emissions and production, generating a classic market failure. According to our results, the current level of emission reduces output by between 0.4 and 0.75%. Notably, these estimates lay in the upper bound of the distribution of those delivered by studies in the early 2000s. To address market failure, governments should step in introducing taxes on emissions. With the tax, brown firms pay a cost for polluting hence facing the incentive to move to green technologies. Governments, however, might also adopt a beggar-thy-neighbour strategy. Reducing emissions is costly, as moves production away from the 'optimal' production mix of brown and green technology. Because emissions are global, a government could just wait for the other country to tackle climate change, ripping the benefits without facing any costs. We study how this strategic game unfolds and show three important results: first, cooperation is first-best optimal from a global prospective; second, countries face incentives to deviate from the cooperating equilibria; third, tariffs on imported brown goods (the only retaliation policy in case of deviation from the cooperation equilibrium) are ineffective because the exchange rate would move to compensate. We finally study monetary policy under when costs for climate change rise and show that the monetary authority should react stronger to deviations of inflation from its target.

Keywords: climate change, general equilibrium, optimal taxation, monetary policy

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Authors: Beth Jacobs

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The landmark movement of Western clinical psychology in the 20th century was the development of psychotherapy. The landmark movement of clinical psychology in the 21st century will be the absorption of meditation practices from Buddhist psychology. While millions of people explore meditation and related philosophy, very few people are exposed to the materials of original Buddhism on this topic, especially to the Theravadan Abhidharma. The Abhidharma is an intricate system of lists and matrixes that were used to understand and remember Buddha’s teaching. The Abhidharma delineates the first psychological system of Buddhism, how the mind works in the universe of reality and why meditation training strengthens and purifies the experience of life. Its lists outline the psychology of mental constructions, perception, emotion and cosmological causation. While the Abhidharma is technical, elaborate and complex, its essential purpose relates to the central purpose of clinical psychology: to relieve human suffering. Like Western depth psychology, the methodology rests on understanding underlying processes of consciousness and perception. What clinical psychologists might describe as therapeutic improvement, the Abhidharma delineates as a specific pathway of purified actions of consciousness. This paper discusses the concept of 'path' as presented in aspects of the Theravadan Abhidharma and relates this to current clinical psychological views of therapy outcomes and gains. The core path in Buddhism is the Eight-Fold Path, which is the fourth noble truth and the launching of activity toward liberation. The path is not composed of eight ordinal steps; it’s eight-fold and is described as opening the way, not funneling choices. The specific path in the Abhidharma is described in many steps of development of consciousness activities. The path is not something a human moves on, but something that moments of consciousness develop within. 'Cittas' are extensively described in the Abhidharma as the atomic-level unit of a raw action of consciousness touching upon an object in a field, and there are 121 types of cittas categorized. The cittas are embedded in the mental factors, which could be described as the psychological packaging elements of our experiences of consciousness. Based on these constellations of infinitesimal, linked occurrences of consciousness, citta are categorized by dimensions of purification. A path is a chain of citta developing through causes and conditions. There are no selves, no pronouns in the Abhidharma. Instead of me walking a path, this is about a person working with conditions to cultivate a stream of consciousness that is pure, immediate, direct and generous. The same effort, in very different terms, informs the work of most psychotherapies. Depth psychology seeks to release the bound, unconscious elements of mental process into the clarity of realization. Cognitive and behavioral psychologies work on breaking down automatic thought valuations and actions, changing schemas and interpersonal dynamics. Understanding how the original Buddhist concept of positive human development relates to the clinical psychological concept of therapy weaves together two brilliant systems of thought on the development of human well being.

Keywords: Abhidharma, Buddhist path, clinical psychology, psychotherapeutic outcome

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Authors: Supriya Majumder, Pabitra Banik

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Fates of Arsenic (As) on the soil-plant environment belong to the critical emerging issue, which in turn to appraises the threatening implications of a human health risk — assessing the dynamics of As in soil solid components are likely to impose its potential availability towards plant uptake. In the present context, we introduced an improved Sequential Extraction Procedure (SEP) questioning to identify solid-phase speciation of As in paddy soil under variable soil environmental conditions during two consecutive seasons of rice cultivation practices. We coupled gradients of water management practices with the addition of fertilizer amendments to assess the changes in a partition of As through a field experimental study during monsoon and post-monsoon season using two rice cultivars. Water management regimes were varied based on the methods of cultivation of rice by Conventional (waterlogged) vis-a-vis System of Rice Intensification-SRI (saturated). Fertilizer amendment through the nutrient treatment of absolute control, NPK-RD, NPK-RD + Calcium silicate, NPK-RD + Ferrous sulfate, Farmyard manure (FYM), FYM + Calcium silicate, FYM + Ferrous sulfate, Vermicompost (VC), VC + Calcium silicate, VC + Ferrous sulfate were selected to construct the study. After harvest, soil samples were sequentially extracted to estimate partition of As among the different fractions such as: exchangeable (F1), specifically sorbed (F2), As bound to amorphous Fe oxides (F3), crystalline Fe oxides (F4), organic matter (F5) and residual phase (F6). Results showed that the major proportions of As were found in F3, F4 and F6, whereas F1 exhibited the lowest proportion of total soil As. Among the nutrient treatment mediated changes on As fractions, the application of organic manure and ferrous sulfate were significantly found to restrict the release of As from exchangeable phase. Meanwhile, conventional practice produced much higher release of As from F1 as compared to SRI, which may substantially increase the environmental risk. In contrast, SRI practice was found to retain a significantly higher proportion of As in F2, F3, and F4 phase resulting restricted mobilization of As. This was critically reflected towards rice grain As bioavailability where the reduction in grain As concentration of 33% and 55% in SRI concerning conventional treatment (p <0.05) during monsoon and post-monsoon season respectively. Also, prediction assay for rice grain As bioavailability based on the linear regression model was performed. Results demonstrated that rice grain As concentration was positively correlated with As concentration in F1 and negatively correlated with F2, F3, and F4 with a satisfactory level of variation being explained (p <0.001). Finally, we conclude that F1, F2, F3 and F4 are the major soil. As fractions critically may govern the potential availability of As in soil and suggest that rice cultivation with the SRI treatment is particularly at less risk of As availability in soil. Such exhaustive information may be useful for adopting certain management practices for rice grown in contaminated soil concerning to the environmental issues in particular.

Keywords: arsenic, fractionation, paddy soil, potential availability

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Authors: Ani Wilson Uchenna, Ogbonna Chikodi

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This study examined the impact of artificial intelligence driven applications on banks’ performance in West Africa using Nigeria and Ghana as case studies. Specifically, the study examined the extent to which deployment of smart automated teller machine impacts the banks’ net worth within the reference period in Nigeria and Ghana. It ascertained the impact of point of sale on banks’ net worth within the reference period in Nigeria and Ghana. Thirdly, it verified the extent to which webpay services can influence banks’ performance in Nigeria and Ghana and finally, determined the impact of mobile pay services on banks’ performance in Nigeria and Ghana. The study used automated teller machine (ATM), Point of sale services (POS), Mobile pay services (MOP) and Web pay services (WBP) as proxies for explanatory variables while Bank net worth was used as explained variable for the study. The data for this study were sourced from central bank of Nigeria (CBN) Statistical Bulletin as well as Bank of Ghana (BoGH) Statistical Bulletin, Ghana payment systems oversight annual report and world development indicator (WDI). Furthermore, the mixed order of integration observed from the panel unit test result justified the use of autoregressive distributed lag (ARDL) approach to data analysis which the study adopted. While the cointegration test showed the existence of cointegration among the studied variables, bound test result justified the presence of long-run relationship among the series. Again, ARDL error correction estimate established satisfactory (13.92%) speed of adjustment from long run disequilibrium back to short run dynamic relationship. The study found that while Automated teller machine (ATM) had statistically significant impact on bank net worth (BNW) of Nigeria and Ghana, point of sale services application (POS) statistically and significantly impact on bank net worth within the study period, mobile pay services application was statistically significant in impacting the changes in the bank net worth of the countries of study while web pay services (WBP) had no statistically significant impact on bank net worth of the countries of reference. The study concluded that artificial intelligence driven application have significant an positive impact on bank performance with exception of web pay which had negative impact on bank net worth. The study recommended that management of banks both in Nigerian and Ghanaian should encourage more investments in AI-powered smart ATMs aimed towards delivering more secured banking services in order to increase revenue, discourage excessive queuing in the banking hall, reduced fraud and minimize error in processing transaction. Banks within the scope of this study should leverage on modern technologies to checkmate the excesses of the private operators POS in order to build more confidence on potential customers. Government should convert mobile pay services to a counter terrorism tool by ensuring that restrictions on over-the-counter withdrawals to a minimum amount is maintained and place sanctions on withdrawals above that limit.

Keywords: artificial intelligence (ai), bank performance, automated teller machines (atm), point of sale (pos)

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Authors: Swati Mishra

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In recent years, there has been an explosion in Gold NanoParticle (GNP) research, with a rapid increase in publications in diverse fields, including imaging, bioengineering, and molecular biology. GNPs exhibit unique physicochemical properties, including surface plasmon resonance (SPR) and bind amine and thiol groups, allowing surface modification and use in biomedical applications. Nanoparticle functionalization is the subject of intense research at present, with rapid progress being made towards developing biocompatible, multi-functional particles. In the present study, the photochemical method has been done to functionalize various-shaped GNPs like nanostars by the molecules like ninhydrin. Ninhydrin is bactericidal, virucidal, fungicidal, antigen-antibody reactive, and used in fingerprint technology in forensics. The GNPs functionalized with ninhydrin efficiently will bind to the amino acids on the target protein, which is of eminent importance during the pandemic, especially where long-term treatments of COVID- 19 bring many side effects of the drugs. The photochemical method is adopted as it provides low thermal load, selective reactivity, selective activation, and controlled radiation in time, space, and energy. The GNPs exhibit their characteristic spectrum, but a distinctly blue or redshift in the peak will be observed after UV irradiation, ensuring efficient ninhydrin binding. Now, the bound ninhydrin in the GNP carrier, upon chemically reacting with any amino acid, will lead to the formation of Rhumann purple. A common method of GNP production includes citrate reduction of Au [III] derivatives such as aurochloric acid (HAuCl4) in water to Au [0] through a one-step synthesis of size-tunable GNPs. The following reagents are prepared to validate the approach. Reagent A solution 1 is0.0175 grams ninhydrin in 5 ml Millipore water Reagent B 30 µl of HAuCl₄.3H₂O in 3 ml of solution 1 Reagent C 1 µl of gold nanostars in 3 ml of solution 1 Reagent D 6 µl of cetrimonium bromide (CTAB) in 3 ml of solution1 ReagentE 1 µl of gold nanostars in 3 ml of ethanol ReagentF 30 µl of HAuCl₄.₃H₂O in 3 ml of ethanol ReagentG 30 µl of HAuCl₄.₃H₂O in 3 ml of solution 2 ReagentH solution 2 is0.0087 grams ninhydrin in 5 ml Millipore water ReagentI 30 µl of HAuCl₄.₃H₂O in 3 ml of water The reagents were irradiated at 254 nm for 15 minutes, followed by their UV Visible spectroscopy. The wavelength was selected based on the one reported for excitation of a similar molecule Pthalimide. It was observed that the solution B and G deviate around 600 nm, while C peaks distinctively at 567.25 nm and 983.9 nm. Though it is tough to say about the chemical reaction happening, butATR-FTIR of reagents will ensure that ninhydrin is not forming Rhumann purple in the absence of amino acids. Therefore, these experiments, we achieved the functionalization of gold nanostars with ninhydrin corroborated by the deviation in the spectrum obtained in a mixture of GNPs and ninhydrin irradiated with UV light. It prepares them as a carrier molecule totake up amino acids for targeted delivery or germicidal action.

Keywords: gold nanostars, ninhydrin, photochemical method, UV visible specgtroscopy

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Authors: Julie Furst-Bowe

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Over the past decade, there has been significant growth in online courses and programs at all levels of education in the United States. This study explores the growth of online and blended (or hybrid) programs offered by the sixteen technical colleges in the Wisconsin Technical College System (WTCS). The WTCS provides education and training programs to more than 300,000 students each year in career clusters including agriculture, business, energy, information technology, healthcare, human services, manufacturing, and transportation. These programs range from short-term training programs that may lead to a certificate to two-year programs that lead to an associate degree. Students vary in age from high school students who are exploring career interests to employees who are seeking to gain additional skills or enter a new career. Because there is currently a shortage of skilled workers in nearly all sectors in the state of Wisconsin, it is critical that the WTCS is providing fully educated and trained graduates to fill workforce needs in a timely manner. For this study, information on online and blended programs for the past five years was collected from the WTCS, including types of programs, course and program enrollments, course completion rates, program completion rates, time to completion and graduate employment rates. The results of this study indicate that the number of online and blended courses and programs is continuing to increase each year. Online and blended programs are most commonly found in the business, human services, and information technology areas, and they are less commonly found in agriculture, healthcare, manufacturing, and transportation programs. Overall, course and program completion rates were higher for blended programs when compared to fully online programs. Students preferred the blended programs over the fully online programs. Overall, graduates were placed into related jobs at a rate of approximately 90 percent, although there was some variation in graduate placement rates by programs and by colleges. Differences in graduate employment rate appeared to be based on geography and sector as employers did not distinguish between graduates who had completed their programs via traditional, blended or fully online instruction. Recommendations include further exploration as to the reasons that blended courses and programs appear to be more effective than fully online courses and programs. It is also recommended that those program areas that are not using blended or online delivery methods, including agriculture, health, manufacturing and transportation, explore the use of these methods to make their courses and programs more accessible to students, particularly working adults. In some instances, colleges were partnering with specific companies to ensure that groups of employees were completing online coursework leading to a certificate or a degree. Those partnerships are to be encouraged in order for the state to continue to improve the skills of its workforce. Finally, it is recommended that specific colleges specialize in the delivery of specific programs using online technology since it is not bound by geographic considerations. This approach would take advantage of the strengths of the individual colleges and avoid unnecessary duplication.

Keywords: career and technical education, online learning, skills shortage, technical colleges

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Authors: Jessie Rapoza, Petr Moroshkin, Jimmy Xu

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Chirality is omnipresent, in nature, in life, and in the field of physics. One intriguing example is the homochirality that has remained a great secret of life. Another is the pairs of mirror-image molecules – enantiomers. They are identical in atomic composition and therefore indistinguishable in the scalar physical properties. Yet, they can be either therapeutic or toxic, depending on their chirality. Recent studies suggest a potential link between abnormal levels of certain D-amino acids and some serious health impairments, including schizophrenia, amyotrophic lateral sclerosis, and potentially cancer. Although indistinguishable in their scalar properties, the chirality of a molecule reveals itself in interaction with the surrounding of a certain chirality, or more generally, a broken mirror-symmetry. In this work, we report on a system for chiral molecule detection, in which the mirror-symmetry is doubly broken, first by asymmetric structuring a nanopatterned plasmonic surface than by the incidence of circularly polarized light (CPL). In this system, the incident circularly-polarized light induces a surface plasmon polariton (SPP) wave, propagating along the asymmetric plasmonic surface. This SPP field itself is chiral, evanescently bound to a near-field zone on the surface (~10nm thick), but with an amplitude greatly intensified (by up to 104) over that of the incident light. It hence probes just the molecules on the surface instead of those in the volume. In coupling to molecules along its path on the surface, the chiral SPP wave favors one chirality over the other, allowing for chirality detection via the change in an optical rectification current measured at the edges of the sample. The asymmetrically structured surface converts the high-frequency electron plasmonic-oscillations in the SPP wave into a net DC drift current that can be measured at the edge of the sample via the mechanism of optical rectification. The measured results validate these design concepts and principles. The observed optical rectification current exhibits a clear differentiation between a pair of enantiomers. Experiments were performed by focusing a 1064nm CW laser light at the sample - a gold grating microchip submerged in an approximately 1.82M solution of either L-arabinose or D-arabinose and water. A measurement of the current output was then recorded under both rights and left circularly polarized lights. Measurements were recorded at various angles of incidence to optimize the coupling between the spin-momentums of the incident light and that of the SPP, that is, spin-momentum locking. In order to suppress the background, the values of the photocurrent for the right CPL are subtracted from those for the left CPL. Comparison between the two arabinose enantiomers reveals a preferential signal response of one enantiomer to left CPL and the other enantiomer to right CPL. In sum, this work reports on the first experimental evidence of the feasibility of chiral molecule detection via optical rectification in a metal meta-grating. This nanoscale interfaced electrical detection technology is advantageous over other detection methods due to its size, cost, ease of use, and integration ability with read-out electronic circuits for data processing and interpretation.

Keywords: Chirality, detection, molecule, spin

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Authors: Chitresh Prasad, Arvind Ramesh, Aditya Virkar, Karan Dholkaria, Vinayak Malhotra

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Solid Propellant Rocket is a rocket that utilises a combination of a solid Oxidizer and a solid Fuel. Success in Solid Rocket Motor design and development depends significantly on knowledge of burning rate behaviour of the selected solid propellant under all motor operating conditions and design limit conditions. Most Solid Motor Rockets consist of the Main Engine, along with multiple Boosters that provide an additional thrust to the space-bound vehicle. Though widely used, they have been eclipsed by Liquid Propellant Rockets, because of their better performance characteristics. The addition of a catalyst such as Iron Oxide, on the other hand, can drastically enhance the performance of a Solid Rocket. This scientific investigation tries to emulate the working of a Solid Rocket using Sparklers and Energized Candles, with a central Energized Candle acting as the Main Engine and surrounding Sparklers acting as the Booster. The Energized Candle is made of Paraffin Wax, with Magnesium filings embedded in it’s wick. The Sparkler is made up of 45% Barium Nitrate, 35% Iron, 9% Aluminium, 10% Dextrin and the remaining composition consists of Boric Acid. The Magnesium in the Energized Candle, and the combination of Iron and Aluminium in the Sparkler, act as catalysts and enhance the burn rates of both materials. This combustion of Metallized Propellants has an influence over the regression rate of the subject candle. The experimental parameters explored here are Separation Distance, Systematically varying Configuration and Layout Symmetry. The major performance parameter under observation is the Regression Rate of the Energized Candle. The rate of regression is significantly affected by the orientation and configuration of the sparklers, which usually act as heat sources for the energized candle. The Overall Efficiency of any engine is factorised by the thermal and propulsive efficiencies. Numerous efforts have been made to improve one or the other. This investigation focuses on the Orientation of Rocket Motor Design to maximize their Overall Efficiency. The primary objective is to analyse the Flame Spread Rate variations of the energized candle, which resembles the solid rocket propellant used in the first stage of rocket operation thereby affecting the Specific Impulse values in a Rocket, which in turn have a deciding impact on their Time of Flight. Another objective of this research venture is to determine the effectiveness of the key controlling parameters explored. This investigation also emulates the exhaust gas interactions of the Solid Rocket through concurrent ignition of the Energized Candle and Sparklers, and their behaviour is analysed. Modern space programmes intend to explore the universe outside our solar system. To accomplish these goals, it is necessary to design a launch vehicle which is capable of providing incessant propulsion along with better efficiency for vast durations. The main motivation of this study is to enhance Rocket performance and their Overall Efficiency through better designing and optimization techniques, which will play a crucial role in this human conquest for knowledge.

Keywords: design modifications, improving overall efficiency, metallized combustion, regression rate variations

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Authors: Jessica Neri, Elena Faccio

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In Europe, except for Denmark and Malta, the legal gender change and the stages of the possible process of gender transition are bound to the diagnosis of a gender identity disorder. The requirement of the evaluation of a mental disorder might have many implications on trans people’s self-representations, interpersonal relations in different social contexts and the therapeutic relations with clinicians during the transition. Psychopathological language may contribute to define the individual’s reality from normative presuppositions with value implications related to the dominant cultural principles. In an effort to mark the boundaries between sanity and pathology, it concurs to the definition of the management procedures of the constructed diversities and deviances, legitimizing the operational practices of particular professional figures. The aim of this research concerns the analysis of the diagnostic category of gender dysphoria contained in the last edition of the Diagnostic and Statistical Manual of Mental Disorders. In particular, this study focuses on the relationship between the implicit and explicit assumptions related to the expressions of gender non-conformity, that sustain the language and the criteria characterizing the Manual, and the possible implications on people’s narratives of transition. In order to achieve this objective two main research methods were used: historical reconstruction of the diagnostic category in the different versions of the Manual and content analysis of that category in the present version. From the historical analysis, in the medical and psychiatric field gender non-conformity has been predominantly explicated by naturalistic perspectives, naming it ‘transsexualism’ and collocating it in the category of gender identity disorder. Currently, pathological judged experiences are represented by gender dysphoria, described in the DSM-5 as the distress that may accompany the incongruence between one's experienced or expressed gender and one's assigned gender, specifying that there must be ‘evidence’ of this. Implicit theories about gender binary, parallelism between gender identity, sex and sexuality and the understanding of the mental health and the subject’s agency as subordinated to the expert knowledge, can be found in the process of designation of the category. A lack of awareness of the historical, social and political aspects connected to the cultural and normative dimensions at the basis of these implicit theories, can be noticed and data given by culture and data given by supposed -biological or psychological- nature, are often confused. This reductionist interpretation of gender and its presumed diversities legitimize the clinician to assume the role of searching and orienting, in a correctional perspective, the biographical elements that correspond to him specific expectations, with no space for other possibilities and identity configurations for people in transition. This research may contribute to the current critical debate about the epistemological foundation of the psychodiagnosis, emphasizing the pragmatic effects on the individuals and on the psychological practice in its wider social context. This work also permits to underline the risks due to the lack of awareness of the processes of social construction of the diagnostic system and its essential role of defence of the values that hold up the symbolic universe of reference.

Keywords: diagnosis, gender dysphoria, narratives, social constructionism

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Authors: Marcus Goh Tian Xi, Alicia Chua Si Wen, Eunice Gan Ghee Wu, Helen Bound, Lee Liang Ying, Albert Lee

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The Map of Dialogical Inquiry provides a conceptual look at the underlying nature of future-oriented skills. According to the Map, learning is learner-oriented, with conversational time shifted from teachers to learners, who play a strong role in deciding what and how they learn. For example, in courses operating on the principles of Dialogical Inquiry, learners were able to leave the classroom with a deeper understanding of the topic, broader exposure to differing perspectives, and stronger critical thinking capabilities, compared to traditional approaches to teaching. Despite its contributions to learning, the Map is grounded in a qualitative approach both in its development and its application for providing feedback to learners and educators. Studies hinge on openended responses by Map users, which can be time consuming and resource intensive. The present research is motivated by this gap in practicality by aiming to develop and validate a quantitative measure of the Map. In addition, a quantifiable measure may also strengthen applicability by making learning experiences trackable and comparable. The Map outlines eight learning aspects that learners should holistically engage. This research focuses on the Analysing aspect of learning. According to the Map, Analysing has four key components: liking or engaging in logic, using interpretative lenses, seeking patterns, and critiquing and deconstructing. Existing scales of constructs (e.g., critical thinking, rationality) related to these components were identified so that the current scale could adapt items from. Specifically, items were phrased beginning with an “I”, followed by an action phrase, to fulfil the purpose of assessing learners' engagement with Analysing either in general or in classroom contexts. Paralleling standard scale development procedure, the 26-item Analysing scale was administered to 330 participants alongside existing scales with varying levels of association to Analysing, to establish construct validity. Subsequently, the scale was refined and its dimensionality, reliability, and validity were determined. Confirmatory factor analysis (CFA) revealed if scale items loaded onto the four factors corresponding to the components of Analysing. To refine the scale, items were systematically removed via an iterative procedure, according to their factor loadings and results of likelihood ratio tests at each step. Eight items were removed this way. The Analysing scale is better conceptualised as unidimensional, rather than comprising the four components identified by the Map, for three reasons: 1) the covariance matrix of the model specified for the CFA was not positive definite, 2) correlations among the four factors were high, and 3) exploratory factor analyses did not yield an easily interpretable factor structure of Analysing. Regarding validity, since the Analysing scale had higher correlations with conceptually similar scales than conceptually distinct scales, with minor exceptions, construct validity was largely established. Overall, satisfactory reliability and validity of the scale suggest that the current procedure can result in a valid and easy-touse measure for each aspect of the Map.

Keywords: analytical thinking, dialogical inquiry, education, lifelong learning, pedagogy, scale development

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Authors: Iorwase Derek Kaka’an, Peter Smolianov, Steven Dion, Christopher Schoen, Jaclyn Norberg, Charles Gabriel Iortimah

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This study examines the current state of football in Nigeria to identify the country's practices, which could be useful internationally, and to determine areas for improvement. Over 200 sources of literature on sport delivery systems in successful sports nations were analyzed to construct a globally applicable model of elite football integrated with mass participation, comprising of the following three levels: macro (socio-economic, cultural, legislative, and organizational), meso (infrastructures, personnel, and services enabling sports programs) and micro level (operations, processes, and methodologies for the development of individual athletes). The model has received scholarly validation and has shown to be a framework for program analysis that is not culturally bound. It has recently been utilized for further understanding such sports systems as US rugby, tennis, soccer, swimming, and volleyball, as well as Dutch and Russian swimming. A questionnaire was developed using the above-mentioned model. Survey questions were validated by 12 experts including academicians, executives from sports governing bodies, football coaches, and administrators. To identify best practices and determine areas for improvement of football in Nigeria, 116 coaches completed the questionnaire. Useful exemplars and possible improvements were further identified through semi-structured discussions with 10 Nigerian football administrators and experts. Finally, a content analysis of the Nigeria Football Federation's website and organizational documentation was conducted. This paper focuses on the micro level of Nigerian football delivery, particularly talent search and development as well as advanced athlete preparation and support. Results suggested that Nigeria could share such progressive practices as the provision of football programs in all schools and full-time coaches paid by governments based on the level of coach education. Nigerian football administrators and coaches could provide better football services affordable for all, where success in mass and elite sports is guided by science focused on athletes' needs. Better implemented could be international best practices such as lifelong guidelines for health and excellence of everyone and integration of fitness tests into player development and ranking as done in best Dutch, English, French, Russian, Spanish, and other European clubs; integration of educational and competitive events for elite and developing athletes as well as fans as done at the 2018 World Cup Russia; and academies with multi-stage athlete nurturing as done by Ajax in Africa as well as Barcelona FC and other top clubs expanding across the world. The methodical integration of these practices into the balanced development of mass and elite football will help contribute to international sports success as well as national health, education, crime control, and social harmony in Nigeria.

Keywords: football, high performance, mass participation, Nigeria, sport development

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Authors: Evren Aysev Denec

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As an urban settlement dating as early as 8000 years and the capital for Byzantine and Ottoman empires; İstanbul has been a significant global city throughout history. The most drastic changes in the macro form of Istanbul have taken place in the last seven decades; starting from 1950’s with rapid industrialization and population growth; pacing up after the 1980’s with the efforts of integration to the global capitalist system; reaching to a climax in the 2000’s with the adaptation of a neoliberal urban regime. Today, the rate of urbanization together with land speculation and real estate investment has been growing enormously. Every inch of urban land is conceptualized as a commodity to be capitalized. This neoliberal mindset has many controversial implementations, from the privatization of public land to the urban transformation of historic neighbourhoods and consumption of natural resources. The planning decisions concerning the city have been mainly top down initiations; conceptualising historical, cultural and natural heritage as commodities to be capitalised and consumed in favour of creating rent value. One of the most crucial implementations of this neoliberal urban regime is the project of establishing a ‘new city’ around northern Istanbul; together with a number of large-scale infrastructural projects such as the Third Bosporus Bridge; a new highway system, a Third Airport Project and a secondary Bosporus project called the ‘Canal Istanbul’. Urbanizing northern Istanbul is highly controversial as this area consists of major natural resources of the city; being the northern forests, water supplies and wildlife; which are bound to be destroyed to a great extent following the implementations. The construction of the third bridge and the third airport has begun in 2013, despite environmental objections and protests. Over five hundred thousand trees are planned be cut for solely the construction of the bridge and the Northern Marmara Motorway. Yet the real damage will be the urbanization of the forest area; irreversibly corrupting the natural resources and attracting millions of additional population towards Istanbul. Furthermore, these projects lack an integrated planning scope as the plans prepared for Istanbul are constantly subjected to alterations forced by the central government. Urban interventions mentioned above are executed despite the rulings of Istanbul Environmental plan, due to top down planning decisions. Instead of an integrated action plan that prepares for the future of the city, Istanbul is governed by partial plans and projects that are issued by a profit based agenda; supported by legal alterations and laws issued by the central government. This paper aims to discuss the ongoing implementations with regards to northern Istanbul; claiming that they are not merely infrastructural interventions but parts of a greater neoliberal urbanization strategy. In the course of the study, firstly a brief account on the northern forests of Istanbul will be presented. Then, the projects will be discussed in detail, addressing how the current planning schemes deal with the natural heritage of the city. Lastly, concluding remarks on how the implementations could affect the future of Istanbul will be presented.

Keywords: Istanbul, urban design, urban planning, natural resources

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Authors: Sabina Huč, Staffan Svensson, Tomaž Hozjan

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Timber structures may be exposed to various environmental conditions during their service life. Often, the structures have to resist extreme changes in the relative humidity of surrounding air, with simultaneously carrying the loads. Wood material response for this load case is seen as increasing deformation of the timber structure. Relative humidity variations cause moisture changes in timber and consequently shrinkage and swelling of the material. Moisture changes and loads acting together result in mechano-sorptive creep, while sustained load gives viscoelastic creep. In some cases, magnitude of the mechano-sorptive strain can be about five times the elastic strain already at low stress levels. Therefore, analyzing mechano-sorptive creep and its influence on timber structures’ long-term behavior is of high importance. Relatively many one-dimensional rheological models for rheological behavior of wood can be found in literature, while a number of models coupling creep response in each material direction is limited. In this study, mathematical formulation of a coupled two-dimensional mechano-sorptive model and its application to the experimental results are presented. The mechano-sorptive model constitutes of a moisture transport model and a mechanical model. Variation of the moisture content in wood is modelled by multi-Fickian moisture transport model. The model accounts for processes of the bound-water and water-vapor diffusion in wood, that are coupled through sorption hysteresis. Sorption defines a nonlinear relation between moisture content and relative humidity. Multi-Fickian moisture transport model is able to accurately predict unique, non-uniform moisture content field within the timber member over time. Calculated moisture content in timber members is used as an input to the mechanical analysis. In the mechanical analysis, the total strain is assumed to be a sum of the elastic strain, viscoelastic strain, mechano-sorptive strain, and strain due to shrinkage and swelling. Mechano-sorptive response is modelled by so-called spring-dashpot type of a model, that proved to be suitable for describing creep of wood. Mechano-sorptive strain is dependent on change of moisture content. The model includes mechano-sorptive material parameters that have to be calibrated to the experimental results. The calibration is made to the experiments carried out on wooden blocks subjected to uniaxial compressive loaded in tangential direction and varying humidity conditions. The moisture and the mechanical model are implemented in a finite element software. The calibration procedure gives the required, distinctive set of mechano-sorptive material parameters. The analysis shows that mechano-sorptive strain in transverse direction is present, though its magnitude and variation are substantially lower than the mechano-sorptive strain in the direction of loading. The presented mechano-sorptive model enables observing real temporal and spatial distribution of the moisture-induced strains and stresses in timber members. Since the model’s suitability for predicting mechano-sorptive strains is shown and the required material parameters are obtained, a comprehensive advanced analysis of the stress-strain state in timber structures, including connections subjected to constant load and varying humidity is possible.

Keywords: mechanical analysis, mechano-sorptive creep, moisture transport model, timber

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Authors: Leigha C. Crout

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This paper will investigate the categorical disregard of the People’s Republic of China (PRC) in establishing and maintaining a baseline standard of civil guarantees for economic migrant women and their dependents. In light of the relative forward strides in terms of policy facilitating the ascension of female workers in China, this oft-invisible subgroup of women remains neglected from the modern-day “iron rice bowl” of the self-identified communist state. This study is being undertaken to rectify the absence of data on this subject and provide a baseline for future studies on the matter, as the human rights of migrants has become an established facet of transnational dialogue and debate. The basic methodology of this research will consist of the evaluation of China’s compliance with its own national guidelines, and the eight international human rights law treaties it has ratified. Data will be extracted and cross-checked from a number of relevant sources to monitor the extent of compliance, including but by no means limited to the United Nations Human Rights Council (UNHRC) Universal Periodic Review (UPR) reports and responses, submissions and responses of international human rights treaty bodies, local and international nongovernmental organizations (NGOs) and their annual reports, and articles and commentaries authored by specialists on the modern state and implementation of Chinese law. Together, these data will illuminate the vast network of compliance that has forced many migrant women to work within situations of extreme economic precarity. The structure will proceed as follows: first, an outline of the current status of migrant workers and the enforcement of stipulated protections will be provided; next, the analysis of the oft-debated regulations directing and the outline of mandatory services guaranteed to external and internal migrants; and finally, a conclusion incorporating various recommendations to improve transparency and gradually decrease the amount of migrant work turned forced labor that typifies the economic migrant experience, especially in the case of women. The internal and international migrant workers in China are bound by different and uncomplimentary systems. The first, which governs Chinese citizens moving to different regions or provinces to find more sustainable employment (internal migrants), is called the hukou (or huji) residency system. This law enforces strict regulation of the movement of peoples, while ensuring that residents of urban areas receive preferential benefits to those received by their so-called “agricultural” resident counterparts. Given the overwhelming presence of the Communist Party of China throughout the vast state, the management of internal migrants and the disregard for foreign domestic workers is, at minimum, a surprising oversight. This paper endeavors to provide a much-needed foundation for future commentary and discussion on the treatment of female migrant workers and their families in the People’s Republic of China.

Keywords: female migrant worker’s rights, the People’s Republic of China, forced labor, Hukou residency system

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Authors: A. K. Tursunova, O. V. Chebonenko, A. Zh. Amirkulova, A. O. Abaildayev, O. A. Sapko, Y. M. Dyo, A. Sh. Utarbaeva

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Fusarium solani and its variants cause root and stem rot of plants. Dry rot is the most common disease of potato tubers during storage. The causative agents of fusariosis in contact with plants behave as antagonists, growth stimulants or parasites. The diversity of host-parasite relationships is explained by the parasite’s ability to produce a wide spectrum of biologically active compounds including toxins, enzymes, oligosaccharides, antibiotic substances, enniatins and gibberellins. Many of these metabolites contribute to the creation of compatible relations; others behave as elicitors, inducing various protective responses in plants. An important part of the strategy for developing plant resistance against pathogens is the activation of protein synthesis to produce protective ‘pathogenesis-related’ proteins. The family of PR-proteins known to confer the most protective response is chitinases (EC 3.2.1.14, Cht) and β-1,3-glucanases (EC 3.2.1.39, Glu). PR-proteins also include a large multigene family of peroxidases (EC 1.11.1.7, Pod), and increased activity of Pod and expression of the Pod genes leads to the development of resistance to a broad class of pathogens. Despite intensive research on the role of PR-proteins, the question of their participation in the mechanisms of formation of the F.solani–S.tuberosum pathosуstem is not sufficiently studied. Our aim was to investigate the effect of different classes of F. solani metabolites on the activity of chitinase, β-1,3-glucanases and peroxidases in tubers of Solanum tuberosum. Metabolite culture filtrate (CF) and cytoplasmic components were fractionated by extraction of the mycelium with organic solvents, salting out techniques, dialysis, column chromatography and ultrafiltration. Protein, lipid, carbohydrate and polyphenolic fractions of fungal metabolites were derived. Using enzymatic hydrolysis we obtained oligo glycans from fungal cell walls with different molecular weights. The activity of the metabolites was tested using potato tuber discs (d = 16mm, h = 5mm). The activity of PR-proteins of tubers was analyzed in a time course of 2–24 hours. The involvement of the analysed metabolites in the modulation of both early non-specific and late related to pathogenesis reactions was demonstrated. The most effective inducer was isolated from the CF (fraction of total phenolic compounds including naphtazarins). Induction of PR-activity by this fraction was: chitinase - 340-360%, glucanase - 435-450%, soluble forms of peroxidase - 400-560%, related forms of peroxidase - 215-237%. High-inducing activity was observed by the chloroform and acetonitrile extracts of the mycelium (induction of chitinase and glucanase activity was 176-240%, of soluble and bound forms of peroxidase - 190-400%). The fraction of oligo glycans mycelium cell walls of 1.2 kDa induced chitinase and β-1,3-glucanase to 239-320%; soluble forms and related peroxidase to 198-426%. Oligo glycans cell walls of 5-10 kDa had a weak suppressor effect - chitinase (21-25%) and glucanase (25-28%) activity; had no effect on soluble forms of peroxidase, but induced to 250-270% activity related forms. The CF polysaccharides of 8.5 kDa and 3.1 kDa inhibited synchronously the glucanase and chitinase specific response in step (after 24 hours at 42-50%) and the step response induced nonspecific peroxidase activity: soluble forms 4.8 -5.2 times, associated forms 1.4-1.6 times.

Keywords: fusarium solani, PR-proteins, peroxidase, solanum tuberosum

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Authors: Rauan Sakenov, Peter Bukovics, Peter Gaszler, Veronika Tokacs-Kollar, Beata Bugyi

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FH2 (formin homology-2) domains of several proteins, collectively known as formins, including DAAM, DAAM1 and mDia1, promote G-actin nucleation and elongation. FH2 domains of these formins exist as oligomers. Chain dimerization by ring structure formation serves as a structural basis for actin polymerization function of FH2 domain. Proper single chain configuration and specific interactions between its various regions are necessary for individual chains to form a dimer functional in G-actin nucleation and elongation. FH1 and WH2 domain-containing formins were shown to behave as intrinsically disordered proteins. Thus, the aim of this research was to study structural dynamics of FH2 domain of DAAM. To investigate structural features of FH2 domain of DAAM, molecular dynamics simulation of chain A of FH2 domain of DAAM solvated in water box in 50 mM NaCl was conducted at temperatures from 293.15 to 353.15K, with VMD 1.9.2, NAMD 2.14 and Amber Tools 21 using 2z6e and 1v9d PDB structures of DAAM was obtained on I-TASSER webserver. Calcium and ATP bound G-actin 3hbt PDB structure was used as a reference protein with well-described structural dynamics of denaturation. Topology and parameter information of CHARMM 2012 additive all-atom force fields for proteins, carbohydrate derivatives, water and ions were used in NAMD 2.14 and ff19SB force field for proteins in Amber Tools 21. The systems were energy minimized for the first 1000 steps, equilibrated and produced in NPT ensemble for 1ns using stochastic Langevin dynamics and the particle mesh Ewald method. Our root-mean square deviation (RMSD) analysis of molecular dynamics of chain A of FH2 domains of DAAM revealed similar insignificant changes of total molecular average RMSD values of FH2 domain of these formins at temperatures from 293.15 to 353.15K. In contrast, total molecular average RMSD values of G-actin showed considerable increase at 328K, which corresponds to the denaturation of G-actin molecule at this temperature and its transition from native, ordered, to denatured, disordered, state which is well-described in the literature. RMSD values of lasso and tail regions of chain A of FH2 domain of DAAM exhibited higher than total molecular average RMSD at temperatures from 293.15 to 353.15K. These regions are functional in intra- and interchain interactions and contain highly conserved tryptophan residues of lasso region, highly conserved GNYMN sequence of post region and amino acids of the shell of hydrophobic pocket of the salt bridge between Arg171 and Asp321, which are important for structural stability and ordered state of FH2 domain of DAAM and its functions in FH2 domain dimerization. In conclusion, higher than total molecular average RMSD values of lasso and post regions of chain A of FH2 domain of DAAM may explain disordered state of FH2 domain of DAAM at temperatures from 293.15 to 353.15K. Finally, absence of marked transition, in terms of significant changes in average molecular RMSD values between native and denatured states of FH2 domain of DAAM at temperatures from 293.15 to 353.15K, can make it possible to attribute these formins to the group of intrinsically disordered proteins rather than to the group of intrinsically ordered proteins such as G-actin.

Keywords: FH2 domain, DAAM, formins, molecular modelling, computational biophysics

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Authors: Ewelina Wisnik, Zsolt Regdon, Kinga Chmielewska, Laszlo Virag, Agnieszka Robaszkiewicz

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Apart from protecting genome, PARP1 has been documented to regulate many intracellular processes inter alia gene transcription by physically interacting with chromatin bound proteins and by their ADP-ribosylation. Our recent findings indicate that expression of PARP1 decreases during the differentiation of human CD34+ hematopoietic stem cells to monocytes as a consequence of differentiation-associated cell growth arrest and formation of E2F4-RBL2-HDAC1-SWI/SNF repressive complex at the promoter of this gene. Since the RBL2 complexes repress genes in a E2F-dependent manner and are widespread in the genome in G0 arrested cells, we asked (a) if RBL2 directly contributes to defining monocyte phenotype and function by targeting gene promoters and (b) if RBL2 controls gene transcription indirectly by repressing PARP1. For identification of genes controlled by RBL2 and/or PARP1,we used primer libraries for surface receptors and TLR signaling mediators, genes were silenced by siRNA or shRNA, analysis of gene promoter occupation by selected proteins was carried out by ChIP-qPCR, while statistical analysis in GraphPad Prism 5 and STATISTICA, ChIP-Seq data were analysed in Galaxy 2.5.0.0. On the list of 28 genes regulated by RBL2, we identified only four solely repressed by RBL2-E2F4-HDAC1-BRM complex. Surprisingly, 24 out of 28 emerged genes controlled by RBL2 were co-regulated by PARP1 in six different manners. In one mode of RBL2/PARP1 co-operation, represented by MAP2K6 and MAPK3, PARP1 was found to associate with gene promoters upon RBL2 silencing, which was previously shown to restore PARP1 expression in monocytes. PARP1 effect on gene transcription was observed only in the presence of active EP300, which acetylated gene promoters and activated transcription. Further analysis revealed that PARP1 binding to MA2K6 and MAPK3 promoters enabled recruitment of EP300 in monocytes, while in proliferating cancer cell lines, which actively transcribe PARP1, this protein maintained EP300 at the promoters of MA2K6 and MAPK3. Genome-wide analysis revealed a similar distribution of PARP1 and EP300 around transcription start sites and the co-occupancy of some gene promoters by PARP1 and EP300 in cancer cells. Here, we described a new RBL2/PARP1/EP300 axis which controls gene transcription regardless of the cell type. In this model cell, cycle-dependent transcription of PARP1 regulates expression of some genes repressed by RBL2 upon cell cycle limitation. Thus, RBL2 may indirectly regulate transcription of some genes by controlling the expression of EP300-recruiting PARP1. Acknowledgement: This work was financed by Polish National Science Centre grants nr DEC-2013/11/D/NZ2/00033 and DEC-2015/19/N/NZ2/01735. L.V. is funded by the National Research, Development and Innovation Office grants GINOP-2.3.2-15-2016-00020 TUMORDNS, GINOP-2.3.2-15-2016-00048-STAYALIVE and OTKA K112336. AR is supported by Polish Ministry of Science and Higher Education 776/STYP/11/2016.

Keywords: retinoblastoma transcriptional co-repressor like 2 (RBL2), poly(ADP-ribose) polymerase 1 (PARP1), E1A binding protein p300 (EP300), monocytes

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Authors: Olga A. Momot, Boris I. Synzynys, Alla A. Oudalova

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Obninsk is situated in the Kaluga region 100 km southwest of Moscow on the left bank of the Protva River. Several enterprises utilizing nuclear energy are operating in the town. A special attention in the region where radiation-hazardous facilities are located has traditionally been paid to radioactive gas and aerosol releases into the atmosphere; liquid waste discharges into the Protva river and groundwater pollution. Municipal intakes involve 34 wells arranged 15 km apart in a sequence north-south along the foot of the left slope of the Protva river valley. Northern and southern water intakes are upstream and downstream of the town, respectively. They belong to river valley intakes with mixed feeding, i.e. precipitation infiltration is responsible for a smaller part of groundwater, and a greater amount is being formed by overflowing from Protva. Water intakes are maintained by the Protva river runoff, the volume of which depends on the precipitation fallen out and watershed area. Groundwater contamination with tritium was first detected in a sanitary-protective zone of the Institute of Physics and Power Engineering (SRC-IPPE) by Roshydromet researchers when realizing the “Program of radiological monitoring in the territory of nuclear industry enterprises”. A comprehensive survey of the SRC-IPPE’s industrial site and adjacent territories has revealed that research nuclear reactors and accelerators where tritium targets are applied as well as radioactive waste storages could be considered as potential sources of technogenic tritium. All the above sources are located within the sanitary controlled area of intakes. Tritium activity in water of springs and wells near the SRC-IPPE is about 17.4 – 3200 Bq/l. The observed values of tritium activity are below the intervention levels (7600 Bq/l for inorganic compounds and 3300 Bq/l for organically bound tritium). The risk has being assessed to estimate possible effect of considered tritium concentrations on human health. Data on tritium concentrations in pipe-line drinking water were used for calculations. The activity of 3H amounted to 10.6 Bq/l and corresponded to the risk of such water consumption of ~ 3·10-7 year-1. The risk value given in magnitude is close to the individual annual death risk for population living near a NPP – 1.6·10-8 year-1 and at the same time corresponds to the level of tolerable risk (10-6) and falls within “risk optimization”, i.e. in the sphere for planning the economically sound measures on exposure risk reduction. To estimate the chemical risk, physical and chemical analysis was made of waters from all springs and wells near the SRC-IPPE. Chemical risk from groundwater contamination was estimated according to the EPA US guidance. The risk of carcinogenic diseases at a drinking water consumption amounts to 5·10-5. According to the classification accepted the health risk in case of spring water consumption is inadmissible. The compared assessments of risk associated with tritium exposure, on the one hand, and the dangerous chemical (e.g. heavy metals) contamination of Obninsk drinking water, on the other hand, have confirmed that just these chemical pollutants are responsible for health risk.

Keywords: radiation-hazardous facilities, water intakes, tritium, heavy metal, health risk

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Authors: Qianxi Lv, Junying Liang

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Among the various modes of interpreting, simultaneous interpreting (SI) is regarded as a ‘complex’ and ‘extreme condition’ of cognitive tasks while consecutive interpreters (CI) do not have to share processing capacity between tasks. Given that SI exerts great cognitive demand, it makes sense to posit that the output of SI may be more compromised than that of CI in the linguistic features. The bulk of the research has stressed the varying cognitive demand and processes involved in different modes of interpreting; however, related empirical research is sparse. In keeping with our interest in investigating the quantitative linguistic factors discriminating between SI and CI, the current study seeks to examine the potential lexical simplification, syntactic complexity and sequential organization mechanism with a self-made inter-model corpus of transcribed simultaneous and consecutive interpretation, translated speech and original speech texts with a total running word of 321960. The lexical features are extracted in terms of the lexical density, list head coverage, hapax legomena, and type-token ratio, as well as core vocabulary percentage. Dependency distance, an index for syntactic complexity and reflective of processing demand is employed. Frequency motif is a non-grammatically-bound sequential unit and is also used to visualize the local function distribution of interpreting the output. While SI is generally regarded as multitasking with high cognitive load, our findings evidently show that CI may impose heavier or taxing cognitive resource differently and hence yields more lexically and syntactically simplified output. In addition, the sequential features manifest that SI and CI organize the sequences from the source text in different ways into the output, to minimize the cognitive load respectively. We reasoned the results in the framework that cognitive demand is exerted both on maintaining and coordinating component of Working Memory. On the one hand, the information maintained in CI is inherently larger in volume compared to SI. On the other hand, time constraints directly influence the sentence reformulation process. The temporal pressure from the input in SI makes the interpreters only keep a small chunk of information in the focus of attention. Thus, SI interpreters usually produce the output by largely retaining the source structure so as to relieve the information from the working memory immediately after formulated in the target language. Conversely, CI interpreters receive at least a few sentences before reformulation, when they are more self-paced. CI interpreters may thus tend to retain and generate the information in a way to lessen the demand. In other words, interpreters cope with the high demand in the reformulation phase of CI by generating output with densely distributed function words, more content words of higher frequency values and fewer variations, simpler structures and more frequently used language sequences. We consequently propose a revised effort model based on the result for a better illustration of cognitive demand during both interpreting types.

Keywords: cognitive demand, corpus-based, dependency distance, frequency motif, interpreting types, lexical simplification, sequential units distribution, syntactic complexity

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Authors: Nabila Farhin, Israt Jahan

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Despite the feminisation of the global health force, women mostly engage in nursing, midwifery and community health workers (HWs), and the posts like surgeons, doctors, and specialists are generally male-dominated. It is also prominent in Bangladesh, where female HWs witness systematic workplace inequalities, discrimination, and underpayment. The Covid-19 pandemic put unsurmountable pressure on HWs as they had to serve in high-risk workplaces as frontliners. The already disadvantaged female HWs shouldered the same burden, were overworked without adequate occupational health and safety measures (OSH) and risked their lives. Acknowledging their vulnerable workplace conditions, the World Health Organization (WHO) and International Labour Organization (ILO) circulated a few specialised guidelines amid the peril. Bangladesh tried to adhere to international guidelines while formulating pandemic management strategies. In reality, the already weak and understaffed health sector collapsed with the patient influx and many HWs got infected and died in the line of duty, exposing the high-risk nature of the work. Unfortunately, the gender-segregated data of infected HWs are absent. This qualitative research investigates whether the existing laws of Bangladesh are adequate in protecting female HWs as frontliners in high-risk workplaces during the Covid-19 pandemic. The paper first examines international labour laws safeguarding female frontline HWs. It also analyses the specialised Covid-19 pandemic guidelines protecting their interests. Finally, the research investigates the compliance of Bangladesh as per international legal guidance during the pandemic. In doing so, it explores the domestic laws, professional guidelines for HWs and pandemic response strategies. The paper critically examines the primary sources like international and national statutes, rules, regulations and guidelines. Secondary sources like authoritative journal articles, books and newspaper reports are contextually analysed in line with the objective of the paper. The definition of HW is ambiguous in the labour laws of Bangladesh. It leads to confusion regarding the extent of legal protection rendered to female HWs at private hospitals in high-risk situations. The labour laws are not applicable in Public hospitals, as the employees follow the public service rules. Unfortunately, the country has no specialised law to protect HWs in high-risk workplaces, and the professional guidelines for HWs also remain inadequate in this regard. Even though the pandemic management strategies highlight some protective measures in high-risk situations, they only deal with HWs who are pregnant or have underlying health issues. No specialised protective guidelines can be found for female HWs as frontliners. Therefore, the laws are insufficient and failed to render adequate legal protection to female frontline HWs during the pandemic. The country also lacks comprehensive health legislation and uniform institutional and professional guidelines, preventing them from accessing grievance mechanisms. Hence, the female HWs felt victimised while duty-bound to serve in high-risk workplaces without adequate safeguards. Bangladesh should clarify the definition of HWs and standardise the service rules for providing medical care in high-risk workplaces. The research also recommends adequate health legislation and specialised legal protection to safeguard female HWs in future emergencies.

Keywords: female health workers (HWs), high-risk workplaces, Covid-19 pandemic, Bangladesh

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Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo

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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.

Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality

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