Tuning NaCo(II) Bimetallic Cooperativity to Perform Co–H Exchange / C–F Bond Activation Processes in Polyfluoroarenes

Recent advances in cooperative chemistry have shown the potential of heterobimetallic complexes combining an alkali-metal with an earth abundant divalent transition metal for the functionalisation of synthetically relevant aromatic molecules via deprotonative metalation. Pairing sodium with cobalt (II), here we provide an overview of the reactivity of bimetallic [NaCo(HMDS)3] [HMDS = N(SiMe3)2] towards C-H and C-F functionalisation of a wide range of perfluorinated molecules. These studies also uncover the enormous potential of this heterobimetallic base to perform Co-H exchanges with excellent selectivity and exceptional stoichiometric control as well as shedding light on the key role played by the alkali-metal

Alkali Metal Metal(ates) Containing Divalent Earth Abundant Transition Metals

Recent advances in cooperative chemistry have shown the enormous potential of main group heterobimetallic complexes for the functionalisation of aromatic molecules. Going beyond main group metal chemistry, here we provide an overview on the synthesis, structure and reactivity of bimetallic complexes which combine an alkali-metal (AM= Li, Na) with a divalent earth-abundant transition metal (M= Mn, Fe, Co, Ni), containing the utility silyl amide HMDS (HMDS = N(SiMe3)2). Advancing the understanding on how cooperative effects operate in these bimetallic (ate) systems, selected examples of their applications in deprotonative metalation are also discussed with special emphasis on the constitution of the metalated intermediates

The external dimension of the EU's fight against transnational crime: Transferring political rationalities of crime control

The article constitutes the first comprehensive review of the EU's export of crime control policies and ‘aid to internal security’ across regions over the last 15 years. Drawing on both International Relations and criminology, it develops an analytical framework to identify the political rationalities and technologies of crime control that the EU attempts to transfer across the Eastern and Southern (extended) neighbourhoods. By scrutinising 216 projects aimed at combating transnational crime beyond Europe's borders, spanning law enforcement, border security, criminal justice, and the penitentiary sector, the empirical analysis is geared towards detecting and systematising the ways of thinking and doing crime control that the EU seeks to promote and export. Moreover, it investigates the ‘action at a distance’ whereby it does so. It is argued that in shaping third countries’ ability to criminalise, police, indict, convict, and punish, the EU is simultaneously defining its own security actorness, specifically consolidating its role as a ‘global crime fighter’

Propranolol as first-line treatment for life-threatening diffuse infantile hepatic hemangioma: a case report

[No abstract available

HDAC4 preserves skeletal muscle structure following long-term denervation by mediating distinct cellular responses

BACKGROUND: Denervation triggers numerous molecular responses in skeletal muscle, including the activation of catabolic pathways and oxidative stress, leading to progressive muscle atrophy. Histone deacetylase 4 (HDAC4) mediates skeletal muscle response to denervation, suggesting the use of HDAC inhibitors as a therapeutic approach to neurogenic muscle atrophy. However, the effects of HDAC4 inhibition in skeletal muscle in response to long-term denervation have not been described yet. METHODS: To further study HDAC4 functions in response to denervation, we analyzed mutant mice in which HDAC4 is specifically deleted in skeletal muscle. RESULTS: After an initial phase of resistance to neurogenic muscle atrophy, skeletal muscle with a deletion of HDAC4 lost structural integrity after 4 weeks of denervation. Deletion of HDAC4 impaired the activation of the ubiquitin-proteasome system, delayed the autophagic response, and dampened the OS response in skeletal muscle. Inhibition of the ubiquitin-proteasome system or the autophagic response, if on the one hand, conferred resistance to neurogenic muscle atrophy; on the other hand, induced loss of muscle integrity and inflammation in mice lacking HDAC4 in skeletal muscle. Moreover, treatment with the antioxidant drug Trolox prevented loss of muscle integrity and inflammation in in mice lacking HDAC4 in skeletal muscle, despite the resistance to neurogenic muscle atrophy. CONCLUSIONS: These results reveal new functions of HDAC4 in mediating skeletal muscle response to denervation and lead us to propose the combined use of HDAC inhibitors and antioxidant drugs to treat neurogenic muscle atrophy

Demand for community-based Case Management in Austria - a qualitative analysis

BACKGROUND: The number of people with complex nursing and care needs living in their own homes is increasing. The implementation of Case and Care Management has shown to have a positive effect on unmet care needs. Research on and implementation of Case and Care Management in the community setting in Austria is limited. This study aimed to understand the changes and challenges of changing care needs by mobile nurses and to evaluate the need for Case Management in mobile care organizations by investigating the evolution of mobile care nurses‘task profiles and the challenges in working in a dynamic field with changing target groups and complexifying care needs. METHODS: A qualitative study with reductive-interpretative data analysis consisting of semi-structured focus groups was conducted. Community care nurses, head nurses, and managers of community mobile care units as well as discharge managers of a community hospital (n = 24) participated in nine qualitative, semi-structured focus groups. The recorded focus groups were transcribed and analyzed using qualitative content analysis. RESULTS: The analysis revealed three main categories: the complexity of the case, innerinstitutional frameworks, and interinstitutional collaboration, which influence the perception of need for further development in the direction of Case and Care Management. Feelings of overwhelmedness among nurses were predominantly tied to cases that presented with issues beyond healthcare such as legal, financial, or social that necessitated communication and collaboration across multiple care providers. CONCLUSIONS: Care institutions need to adapt to changing and increasingly complex care needs that necessitate cooperation between organizations within and across the health and social sectors. A key facilitator for care coordination and the adequate service provision for complex care needs are multidisciplinary institutional networks, which often remain informal, leaving nurses in the role of petitioner without equal footing. Embedding Case and Care Management in the community has the potential to fill this gap and facilitate flexible, timely, and coordinated care across multiple care providers. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1186/s12912-021-00775-0

Secondary metabolites in grapevine: crosstalk of transcriptional, metabolic and hormonal signals controlling stress defence responses in berries and vegetative organs

Abiotic stresses, such as temperature, heat waves, water limitation, solar radiation and the increase in atmospheric CO concentration, significantly influence the accumulation of secondary metabolites in grapevine berries at different developmental stages, and in vegetative organs. Transcriptional reprogramming, miRNAs, epigenetic marks and hormonal crosstalk regulate the secondary metabolism of berries, mainly the accumulation of phenylpropanoids and of volatile organic compounds (VOCs). Currently, the biological mechanisms that control the plastic response of grapevine cultivars to environmental stress or that occur during berry ripening have been extensively studied in many worlds viticultural areas, in different cultivars and in vines grown under various agronomic managements. A novel frontier in the study of these mechanisms is the involvement of miRNAs whose target transcripts encode enzymes of the flavonoid biosynthetic pathway. Some miRNA-mediated regulatory cascades, post-transcriptionally control key MYB transcription factors, showing, for example, a role in influencing the anthocyanin accumulation in response to UV-B light during berry ripening. DNA methylation profiles partially affect the berry transcriptome plasticity of different grapevine cultivars, contributing to the modulation of berry qualitative traits. Numerous hormones (such as abscisic and jasmomic acids, strigolactones, gibberellins, auxins, cytokynins and ethylene) are involved in triggering the vine response to abiotic and biotic stress factors. Through specific signaling cascades, hormones mediate the accumulation of antioxidants that contribute to the quality of the berry and that intervene in the grapevine defense processes, highlighting that the grapevine response to stressors can be similar in different grapevine organs. The expression of genes responsible for hormone biosynthesis is largely modulated by stress conditions, thus resulting in the numeourous interactions between grapevine and the surrounding environment