Activation and discovery of earth-abundant metal catalysts using sodium tert-butoxide

First-row, earth-abundant metals offer an inexpensive and sustainable alternative to precious-metal catalysts. As such, iron and cobalt catalysts have garnered interest as replacements for alkene and alkyne hydrofunctionalization reactions. However, these have required the use of air- and moisture-sensitive catalysts and reagents, limiting both adoption by the non-expert as well as applicability, particularly in industrial settings. Here, we report a simple method for the use of earth-abundant metal catalysts by general activation with sodium tert-butoxide. Using only robust air- and moisture-stable reagents and pre-catalysts, both known and, significantly, novel catalytic activities have been successfully achieved, covering hydrosilylation, hydroboration, hydrovinylation, hydrogenation and [2π+2π] alkene cycloaddition. This activation method allows for the easy use of earth-abundant metals, including iron, cobalt, nickel and manganese, and represents a generic platform for the discovery and application of non-precious metal catalysis

The role of sleep in emotional processing

Abstract In this chapter, we have reviewed an extensive literature supporting the 4 critical role of sleep for several aspects of emotional processing and regulation. In the first part, we discussed the main behavioral and psychophysiological studies that examined how sleep influences the processes of encoding and consolidation of emotional memory. In addition, we examined how sleep modulates emotion regulation, emotional reactivity, and empathy. Further, we discussed the implication of sleep in fear conditioning memory, threat generalization, and extinction memory. In the second part, we discussed evidence specifically suggesting the implication of REM sleep in the consolidation of emotional memory and in the modulation of emotional reactivity. In particular, we will focus on the specific physiological REM features that contributed to suggest its critical involvement in emotional processing. In the third part, we overviewed the functional neuroimaging studies on the brain mechanisms that underlie the relations between sleep and emotions. Finally, we focused on the most important psychiatric disorders that express abnormalities of sleep and emotional alterations, briefly reviewing our knowledge about the relationships between sleep disturbances and mood in major depression, anxiety disorders, and post-traumatic stress disorder. We showed that sleep helps in the formation of emotional memories at every stage of this process. On the contrary, sleep loss induces deficit in encoding of emotional information, leading to a disruptive interference with emotional memory consolidation. The reviewed literatures clearly suggest that sleep loss significantly influences emotional reactivity. Whether sleep acts to protect, potentiate, or de-potentiate emotional reactivity is, however, still debatable. Future studies will have to elucidate, at the behavioral level, the specific direction of the sleep-dependent emotional modulation. Sleep seems to be crucial also for our ability to correctly process emotional information that allows us to understand the others’ feelings and to be empathic with them, as well as for our ability to encode and consolidate fear conditioning and extinction learning. As far as the role of REM sleep is concerned, it seems to be crucial for the consolidation of emotional memory, while its specific contribution on next-day emotional reactivity is less clear. In fact, REM sleep could act to potentiate or, conversely, de-potentiate the emotional charge associated to a memory along with its consolidation. This topic could be also relevant for its implications in clinical settings. Indeed, further explaining how sleep influences the next-day emotional brain functioning will be crucial to open a new perspective for the understanding and treatment of affective or anxiety disturbances in patients with disturbed sleep