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The molecular complexes described herein use main‐group elements or transition metals to control the stoichiometric cleavage of N−H bonds of ammonia (NH₃) and/or catalyze chemical and electrochemical NH₃oxidation to dinitrogen (N₂). We highlight the phenomenon of coordination‐induced bond weakening and a variety of N−H bond cleavage mechanisms of NH₃including H atom abstraction, inter‐ and intra‐molecular deprotonation reactions, oxidative addition, andσ‐bond metathesis that have been demonstrated with molecular systems. We provide an overview of the molecular complexes reported for the rapidly developing field of NH₃oxidation catalysis to form N₂. These systems exhibit several diverse structure types and innovative ligands to support transition metals capable of activating NH₃and mediating a challenging chemical transformation that requires breaking strong N−H bonds and forming an N−N bond en route to N₂formation.

 

The signed value and unsigned salience of reward prediction errors (RPEs) are critical to understanding reinforcement learning (RL) and cognitive control. Dorsomedial prefrontal cortex (dMPFC) and insula (INS) are key regions for integrating reward and surprise information, but conflicting evidence for both signed and unsigned activity has led to multiple proposals for the nature of RPE representations in these brain areas. Recently developed RL models allow neurons to respond differently to positive and negative RPEs. Here, we use intracranially recorded high frequency activity (HFA) to test whether this flexible asymmetric coding strategy captures RPE coding diversity in human INS and dMPFC. At the region level, we found a bias towards positive RPEs in both areas which paralleled behavioral adaptation. At the local level, we found spatially interleaved neural populations responding to unsigned RPE salience and valence-specific positive and negative RPEs. Furthermore, directional connectivity estimates revealed a leading role of INS in communicating positive and unsigned RPEs to dMPFC. These findings support asymmetric coding across distinct but intermingled neural populations as a core principle of RPE processing and inform theories of the role of dMPFC and INS in RL and cognitive control.

 

ABSTRACT We present two mixing models for post-processing of 3D hydrodynamic simulations applied to convective–reactive i-process nucleosynthesis in a rapidly accreting white dwarf (RAWD) with [Fe/H] = −2.6, in which H is ingested into a convective He shell. A 1D advective two-stream model adopts physically motivated radial and horizontal mixing coefficients constrained by 3D hydrodynamic simulations. A simpler approach uses diffusion coefficients calculated from the same simulations. All 3D simulations include the energy feedback of the 12C(p, γ)13N reaction from the H entrainment. Global oscillations of shell H ingestion in two of the RAWD simulations cause bursts of entrainment of H and non-radial hydrodynamic feedback. With the same nuclear network as in the 3D simulations, the 1D advective two-stream model reproduces the rate and location of the H burning within the He shell closely matching the 3D simulation predictions, as well as qualitatively displaying the asymmetry of the XH profiles between the upstream and downstream. With a full i-process network the advective mixing model captures the difference in the n-capture nucleosynthesis in the upstream and downstream. For example, 89Kr and 90Kr with half-lives of $3.18\,\,\mathrm{\mathrm{min}}$ and $32.3\,\,\mathrm{\mathrm{s}}$ differ by a factor 2–10 in the two streams. In this particular application the diffusion approach provides globally the same abundance distribution as the advective two-stream mixing model. The resulting i-process yields are in excellent agreement with observations of the exemplary CEMP-r/s star CS31062-050. 

We report a nickel complex for catalytic oxidation of ammonia to dinitrogen under ambient conditions. Using the aryloxyl radical 2,4,6‐tri‐tert‐butylphenoxyl (^tBu₃ArO⋅) as a H atom acceptor to cleave the N−H bond of a coordinated NH₃ligand up to 56 equiv of N₂per Ni center can be generated. Employing theN‐oxyl radical 2,2,6,6‐(tetramethylpiperidin‐1‐yl)oxyl (TEMPO⋅) as the H‐atom acceptor, up to 15 equiv of N₂per Ni center are formed. A bridging Ni‐hydrazine product identified by isotopic nitrogen (¹⁵N) studies and supported by computational models indicates the N−N bond forming step occurs by bimetallic homocoupling of two paramagnetic [Ni]−NH₂fragments. Ni‐mediated hydrazine disproportionation to N₂and NH₃completes the catalytic cycle.

 

We report a nickel complex for catalytic oxidation of ammonia to dinitrogen under ambient conditions. Using the aryloxyl radical 2,4,6‐tri‐tert‐butylphenoxyl (^tBu₃ArO⋅) as a H atom acceptor to cleave the N−H bond of a coordinated NH₃ligand up to 56 equiv of N₂per Ni center can be generated. Employing theN‐oxyl radical 2,2,6,6‐(tetramethylpiperidin‐1‐yl)oxyl (TEMPO⋅) as the H‐atom acceptor, up to 15 equiv of N₂per Ni center are formed. A bridging Ni‐hydrazine product identified by isotopic nitrogen (¹⁵N) studies and supported by computational models indicates the N−N bond forming step occurs by bimetallic homocoupling of two paramagnetic [Ni]−NH₂fragments. Ni‐mediated hydrazine disproportionation to N₂and NH₃completes the catalytic cycle.

 

Alzheimer’s disease (AD) is the most common neurodegenerative disorder affecting the elderly population worldwide. Brain inflammation plays a key role in the progression of AD. Deposition of senile plaques in the brain stimulates an inflammatory response with the overexpression of pro-inflammatory mediators, such as the neuroinflammatory cytokine. interleukin-6. Curcumin has been revealed to be a potential agent for treating AD following different neuroprotective mechanisms, such as inhibition of aggregation and decrease in brain inflammation. We synthesized new curcumin derivatives with the aim of providing good anti-aggregation capacity but also improved anti-inflammatory activity. Nine curcumin derivatives were synthesized by etherification and esterification of the aromatic region. From these derivatives, compound 8 exhibited an anti-inflammatory effect similar to curcumin, while compounds 3, 4, and 10 were more potent. Moreover, when the anti-aggregation activity is considered, compounds 3, 4, 5, 6, and 10 showed biological activity in vitro. Compound 4 exhibited a strong anti-aggregation effect higher than curcumin. Monofunctionalized curcumin derivatives showed better bioactivity than difunctionalized compounds. Moreover, the presence of bulky groups in the chemical structure of curcumin derivatives decreased bioactivity.