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    Triply bonded pancake π-dimers stabilized by tetravalent actinides

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    Aromatic π-stacking is a weakly attractive, noncovalent interaction often found in biological macromolecules and synthetic supramolecular chemistry. The weak nondirectional nature of π-stacking can present challenges in the design of materials owing to their weak, nondirectional nature. However, when aromatic π-systems contain an unpaired electron, stronger attraction involving face-to-face π-orbital overlap is possible, resulting in covalent so-called “pancake” bonds. Two-electron, multicenter single pancake bonds are well known, whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by a 3-fold reduction of hexaazatrinaphthylene (HAN) and subsequent stacking of the [HAN]3– triradicals. Our analysis reveals a multicenter covalent triple pancake bond consisting of a σ-orbital and two equivalent π-orbitals. An electrostatic stabilizing role is established for the tetravalent thorium and uranium ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of triply bonded π-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials

    Resistance and prevention: Rural local government and the fight against tuberculosis

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    With Wales considered ‘the blackest spot on the tuberculosis map’ of Britain, the Welsh National Memorial Association (WNMA) was founded in 1910 with the aim to rid Wales of the disease within a generation. Although the Association’s vision of a national health service was lauded by contemporaries as providing a model for England, as the WNMA took over the running of tuberculosis services from local authorities, it met with resistance from county and rural district councils. This essay explores this resistance. In placing the views and work of county and rural district councils at the centre of analysis this essay uses Wales and opposition to the WNMA as a case study to rethink the marginalization of county councils and rural district councils in histories of local government, public health, and housing policy in a pivotal period of central-location relations. As this essay shows, the opposition county and rural district councils expressed to the WNMA was not a straightforward rejection of centralization by authorities on the margins of “the modern”. Rather, they put forward a competing vision of health and social welfare that championed local autonomy and a strategy of prevention focused on the material and domestic environment and housing reform. As the essay shows, opponents of the WNMA were not backwoodsmen. They were part of a wider national and progressive social reform movement

    Modification of Huntington's disease by short tandem repeats

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    Expansions of glutamine-coding CAG trinucleotide repeats cause a number of neurodegenerative diseases, including Huntington's disease (HD) and several of the spinocerebellar ataxias (SCAs). In general, age-at-onset of the polyglutamine diseases is inversely correlated with the size of the respective inherited expanded CAG repeat. Expanded CAG repeats are also somatically unstable in certain tissues, and age-at-onset of HD corrected for individual HTT CAG repeat length (i.e., residual age-at-onset), is modified by repeat instability-related DNA maintenance/repair genes as demonstrated by recent genome-wide association studies (GWAS). Modification of one polyglutamine disease (e.g., HD) by the repeat length of another (e.g., ATXN3, CAG expansions in which cause SCA3) has also been hypothesized. Consequently, we determined whether age-at-onset in HD is modified by the CAG repeats of other polyglutamine disease genes. We found that the CAG measured repeat sizes of other polyglutamine disease genes were polymorphic in HD participants but did not influence HD age-at-onset. Additional analysis focusing specifically on ATXN3 in a larger sample set (n = 1,388) confirmed the lack of association between HD residual age-at-onset and ATXN3 CAG repeat length. Additionally, neither our HD onset modifier GWAS single nucleotide polymorphism (SNP) data nor imputed short tandem repeat (STR) data supported involvement of other polyglutamine disease genes in modifying HD. By contrast, our GWAS based on imputed STRs revealed significant modification signals for other genomic regions. Together, our STR GWAS show that modification of HD is associated with STRs that do not involve other polyglutamine disease-causing genes, refining the landscape of HD modification and highlighting the importance of rigorous data analysis, especially in genetic studies testing candidate modifiers

    Integrating sustainable development goals into the architecture curriculum: Experiences and perspectives

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    The Sustainable Development Goals (SDGs) play a crucial role in architectural education, as buildings contribute 39% of global energy-related carbon emissions and 40% of extracted materials are used in construction. This research investigates the current status of SDG integration in architecture education, its challenges, and potential future advancements. A qualitative survey was conducted among architecture educators from 22 institutions across nine countries, focusing on four key aspects: (i) general knowledge and understanding of the SDGs; (ii) qualification and experience regarding the SDGs; (iii) integration of the SDGs in architecture education; and (iv) implementation of the SDGs in architectural practises. The findings revealed that most educators did not receive formal education focused on the SDGs, relying on self-exposure and self-learning. SDG 11 was the most adopted, focusing on improving slum areas, providing safe housing, and promoting sustainable urban settlements while preserving cultural heritage

    Design, synthesis, and evaluation of an anti‐trypanosomal [1,2,4]triazolo[1,5‐ a ]pyrimidine probe for photoaffinity labeling studies

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    Studies have shown that depending on the substitution pattern, microtubule (MT)‐targeting 1,2,4‐triazolo[1,5‐a]pyrimidines (TPDs) can produce different cellular responses in mammalian cells that may be due to these compounds interacting with distinct binding sites within the MT structure. Selected TPDs are also potently bioactive against the causative agent of human African trypanosomiasis, Trypanosoma brucei, both in vitro and in vivo. So far, however, there has been no direct evidence of tubulin engagement by these TPDs in T. brucei. Therefore, to enable further investigation of anti‐trypanosomal TPDs, a TPD derivative amenable to photoaffinity labeling (PAL) was designed, synthesized, and evaluated in PAL experiments using HEK293 cells and T. brucei. The data arising confirmed specific labeling of T. brucei tubulin. In addition, proteomic data revealed differences in the labeling profiles of tubulin between HEK293 and T. brucei, suggesting structural differences between the TPD binding site(s) in mammalian and trypanosomal tubulin

    Weather and climate data for energy applications

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    Weather information plays a critical role in energy applications — from designing and planning to the management and maintenance of building energy systems, renewable energy applications, and smart utility grids. This research examines weather and climate data for energy applications, covering their sources, generation, implementation, and forecasting. Drivers for the use of weather data, data acquisition methods, and parameter characteristics, as well as their impact on energy applications, are critically reviewed. The study also analyses weather data availability from 32 commonly used online sources, considering their cost, features, and resolution. A comprehensive weather data classification is developed based on measurement type, information period, data resolution, and time horizon. The findings indicate that real-time local weather data with high temporal resolution is crucial for optimal energy management and accurate forecasting of energy and environmental behaviours. However, limitations and uncertainties exist in weather data from online sources, particularly for developing countries, due to the limited spatio-temporal coverage

    Indigenous peoples and land-Based disputes: Paraguay and the Paĩ Tavyterã

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    This article discusses some of the long-term tendencies of the Paraguayan political economy, focusing, in particular, on impacts on indigenous peoples and, because of the ongoing agribusiness expansion in the northeast of the country, on the Paĩ Tavyterã nation. This analysis is warranted because of the growing recognition of the importance of land-related disputes affecting indigenous peoples, particularly in countries such as Paraguay that rely heavily on agribusiness exports and on the exploitation of natural resources. It is based on more than six years of research dedicated to the land struggles of the Paĩ Tavyterã (and members of the same ethnic group in Brazil, called Guarani-Kaiowa). Instead of a comparative study, this is a relational storytelling text that draws insights from various actors, communities and situations that were obtained through a qualitative and participative methodology, involving indigenous communities as co-participants and co-investigators in the study. Empirical results demonstrate that, despite the fact that Paraguay is a major exporter of agribusiness commodities the accumulation of multiple forms of subtraction is a prevailing geographical force. The reaction of indigenous peoples is in the form of anti-subtraction. The main implication of this research is that the process of decolonisation is, first and foremost, an anti-subtraction movement that aims to revert the deficit caused by the systemic subtraction of socio-economic and socio-ecological opportunities

    Optimisation of livestock routing on farms

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    A grass-based livestock farm will typically be partitioned into a set of fields which may not be contiguous. The livestock in question will be distributed among these fields plus a set of buildings. This distribution will change over time as a result of livestock being routed between different locations. This change in distribution is not a random process. It is instead planned by the farmer to satisfy a set of constraints while minimising workload. The set of constraints in question are designed to maximise the performance of the farm and, in many cases, will be large. In this work, we refer to the above planning problem as the \emph{Livestock Routing Problem} (LRP). We propose modelling the LRP as an integer program, which is a specific type of mathematical optimisation problem. Our model is general in nature whereby many farming activities can be incorporated. These activities include rotational grazing, silage production and livestock breeding. In our analysis we consider many different instances of the LRP and attempt to solve these instances using an off-the-shelf integer program solver. In most cases, an optimal or close to optimal solution is found in reasonable time. These results demonstrate that the proposed methods could be used within a decision support system for livestock farmers and, in turn, reduce the workload associated with the routing of livestock

    Atypical cortical networks in children at high-genetic risk of psychiatric and eurodevelopmental disorders

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    Although many genetic risk factors for psychiatric and neurodevelopmental disorders have been identified, the neurobiological route from genetic risk to neuropsychiatric outcome remains unclear. 22q11.2 deletion syndrome (22q11.2DS) is a copy number variant (CNV) syndrome associated with high rates of neurodevelopmental and psychiatric disorders including autism spectrum disorder (ASD), attention deficit hyperactivity disorder (ADHD) and schizophrenia. Alterations in neural integration and cortical connectivity have been linked to the spectrum of neuropsychiatric disorders seen in 22q11.2DS and may be a mechanism by which the CNV acts to increase risk. In this study, magnetoencephalography (MEG) was used to investigate electrophysiological markers of local and global network function in 34 children with 22q11.2DS and 25 controls aged 10–17 years old. Resting-state oscillatory activity and functional connectivity across six frequency bands were compared between groups. Regression analyses were used to explore the relationships between these measures, neurodevelopmental symptoms and IQ. Children with 22q11.2DS had altered network activity and connectivity in high and low frequency bands, reflecting modified local and long-range cortical circuitry. Alpha and theta band connectivity were negatively associated with ASD symptoms while frontal high frequency (gamma band) activity was positively associated with ASD symptoms. Alpha band activity was positively associated with cognitive ability. These findings suggest that haploinsufficiency at the 22q11.2 locus impacts short and long-range cortical circuits, which could be a mechanism underlying neurodevelopmental and psychiatric vulnerability in this high-risk group

    Blockchain for energy efficiency training in the construction industry

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    The construction sector faces the urgent need to prioritize energy efficiency due to an increasingly stringent regulatory landscape in response to the climate change agenda. Central to this transition is the pivotal role of education in equipping professionals with the necessary knowledge and skills. Educational solutions have emerged as powerful tools for promoting awareness and interventions to mitigate climate change. This article provides a case study that highlights the successful utilisation of computer technology in delivering digital solutions to advance energy education and promote more informed energy practices in the construction industry. The utilisation of digital technologies can enhance collaborative efforts in energy efficiency training, which is of critical significance in ensuring the security, sovereignty, transparency, immutability, and decentralisation of interventions related to energy education. This paper presents a framework that utilises Blockchain technology to facilitate training labelling and authenticity based on smart contracts and mobile passports to provide a secure and efficient solution for the delivery of training and education in the energy domain. Our research examines the challenges and opportunities related to energy efficiency training within the construction industry. By integrating industry-specific insights, exemplifications, and case studies, we provide an in-depth understanding of the interconnection between energy efficiency education and digital solutions with the unique context of the construction industry. We underscore the importance of leveraging digital platforms as educational tools to foster a deeper understanding and adoption of energy-efficient practices. We demonstrate that educational solutions play a pivotal role in driving awareness and interventions for mitigating climate change, greatly empowering individuals and organizations to adopt energy-efficient practices and to address sustainability objectives

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