Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst

The pincer d8-monohydride complex RhH{xant(PiPr2)2} (xant(PiPr2)2 = 9, 9-dimethyl-4, 5-bis(diisopropylphosphino)xanthene) promotes the release of 1 equiv of hydrogen from H3BNH3 and H3BNHMe2 with TOF50% values of 3150 and 1725 h–1, to afford [BH2NH2]n and [BH2NMe2]2 and the tandem ammonia borane dehydrogenation–cyclohexene hydrogenation. DFT calculations on the ammonia borane dehydrogenation suggest that the process takes place by means of cis-¿2-PP-species, through four stages including: (i) Shimoi-type coordination of ammonia borane, (ii) homolytic addition of the coordinated H–B bond to afford a five-coordinate dihydride-boryl-rhodium(III) intermediate, (iii) reductive intramolecular proton transfer from the NH3 group to one of the hydride ligands, and (iv) release of H2 from the resulting square-planar hydride dihydrogen rhodium(I) intermediate

Early socialization and environmental enrichment of lactating piglets affects the caecal microbiota and metabolomic response after weaning

The aim of this study was to determine the possible impact of early socialization and an enriched neonatal environment to improve adaptation of piglets to weaning. We hypothesized that changes in the microbiota colonization process and in their metabolic response and intestinal functionality could help the animals face weaning stress. A total of 48 sows and their litters were allotted into a control (CTR) or an enriched treatment (ENR), in which piglets from two adjacent pens were combined and enriched with toys. The pattern of caecal microbial colonization, the jejunal gene expression, the serum metabolome and the intestinal physiology of the piglets were assessed before (-2 d) and after weaning (+ 3d). A differential ordination of caecal microbiota was observed after weaning. Serum metabolome suggested a reduced energetic metabolism in ENR animals, as evidenced by shifts in triglycerides and fatty acids, VLDL/LDL and creatine regions. The TLR2 gene showed to be downregulated in the jejunum of ENR pigs after weaning. The integration of gene expression, metabolome and microbiota datasets confirmed that differences between barren and enriched neonatal environments were evident only after weaning. Our results suggest that improvements in adaptation to weaning could be mediated by a better response to the post-weaning stress.info:eu-repo/semantics/publishedVersio

Control of crystal size tailors the electrochemical performance of alpha-V2O5 as a Mg2+ intercalation host

α-V2O5 has been extensively explored as a Mg2+ intercalation host with potential as a battery cathode, offering high theoretical capacities and potentials vs. Mg2+/Mg. However, large voltage hysteresis is observed with Mg insertion and extraction, introducing significant and unacceptable round-trip energy losses with cycling. Conventional interpretations suggest that bulk ion transport of Mg2+ within the cathode particles is the major source of this hysteresis. Herein, we demonstrate that nanosizing α-V2O5 gives a measurable reduction to voltage hysteresis on the first cycle that substantially raises energy efficiency, indicating that mechanical formatting of the α-V2O5 particles contributes to hysteresis. However, no measurable improvement in hysteresis is found in the nanosized α-V2O5 in latter cycles despite the much shorter diffusion lengths, suggesting that other factors aside from Mg transport, such as Mg transfer between the electrolyte and electrode, contribute to this hysteresis. This observation is in sharp contrast to the conventional interpretation of Mg electrochemistry. Therefore, this study uncovers critical fundamental underpinning limiting factors in Mg battery electrochemistry, and constitutes a pivotal step towards a high-voltage, high-capacity electrode material suitable for Mg batteries with high energy density

Enhanced charge storage of nanometric ζ-V₂O₅ in Mg electrolytes

V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g−1) compared to bulk ζ-V2O5 (70 mA h g−1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases

Prox1 Regulates the Notch1-Mediated Inhibition of Neurogenesis

During development of the spinal cord, Prox1 controls the balance between proliferation and differentiation of neural progenitor cells via suppression of Notch1 gene expression

The Role of Response Elements Organization in Transcription Factor Selectivity: The IFN-β Enhanceosome Example

What is the mechanism through which transcription factors (TFs) assemble specifically along the enhancer DNA? The IFN-β enhanceosome provides a good model system: it is small; its components' crystal structures are available; and there are biochemical and cellular data. In the IFN-β enhanceosome, there are few protein-protein interactions even though consecutive DNA response elements (REs) overlap. Our molecular dynamics (MD) simulations on different motif combinations from the enhanceosome illustrate that cooperativity is achieved via unique organization of the REs: specific binding of one TF can enhance the binding of another TF to a neighboring RE and restrict others, through overlap of REs; the order of the REs can determine which complexes will form; and the alternation of consensus and non-consensus REs can regulate binding specificity by optimizing the interactions among partners. Our observations offer an explanation of how specificity and cooperativity can be attained despite the limited interactions between neighboring TFs on the enhancer DNA. To date, when addressing selective TF binding, attention has largely focused on RE sequences. Yet, the order of the REs on the DNA and the length of the spacers between them can be a key factor in specific combinatorial assembly of the TFs on the enhancer and thus in function. Our results emphasize cooperativity via RE binding sites organization

EHLA research team wins renowned Berthold Leibinger Innovationspreis 2018

The research team of the Fraunhofer Institute for Laser Technology ILT and the Chair of Digital Additive Production DAP of RWTH Aachen University will be honored with the Berthold Leibinger Innovationspreis 2018 for their development of the “Extreme High-Speed Laser Material Deposition” (EHLA). This process can be used to coat, repair or additively manufacture components in a particularly economical and environmentally friendly way. On September 21, the Aachen scientists will receive the first prize of the laser innovation prize awarded by the private foundation Berthold Leibinger Stiftung in Ditzingen, Germany, every other year since 2000 for outstanding research and development on the application or generation of laser light. The timing was simply right: The research team heard on May 16, 2018 – the first International Day of Light – that it was invited to the jury session in Ditzingen as a finalist. On July 13, 2018, Thomas Schopphoven (Fraunhofer ILT) represented the team which includes his colleagues Andres Gasser (also Fraunhofer ILT) and Gerhard Maria Backes (Chair of Digital Additive Production DAP, RWTH Aachen University). He presented and explained their innovation alongside seven other finalist teams from all over the world

Ca(BH4)2 + MgH2: Desorption Reaction and Role of Mg on Its Reversibility

The Ca(BH4)2–MgH2 composite system represents a promising candidate for mobile hydrogen storage due to a 10.5 wt % theoretical hydrogen storage capacity and an estimated equilibrium temperature lower than 160 °C. For this system, the reversibility was achieved without further addition of additives. In this study, the decomposition path of the Ca(BH4)2 + MgH2 composite system is investigated in detail by in situ synchrotron radiation powder X-ray diffraction and differential scanning calorimetry combined with thermogravimetry. The sorption properties are analyzed by volumetric measurements. 11B{1H} solid state magic angle spinning–nuclear magnetic resonance was employed for the characterization of the final amorphous or nanocrystalline boron-based decomposition products. This study shows that the intermediate formation of Ca4Mg3H14 upon dehydrogenation of the Ca(BH4)2–MgH2 composite system is not a necessary step, and its presence can be adjusted modifying the preparation procedure. Moreover, the d-value mismatch calculated for the {111}CaB6/{1011}Mg plane pair is the lowest among the other plane pairs considered in the system. The mismatch in the third direction between CaB6 and Mg is also extremely good. These findings propose Mg as a supporter of the heterogeneous nucleation of CaB6 during decomposition of the Ca(BH4)2 + MgH2 composite system

Understanding host-microbiota interactions in the commercial piglet around weaning

Weaning is a critical period in the life of pigs with repercussions on their health and welfare and on the economy of the swine industry. This study aimed to assess the efect of the commercial early weaning on gut microbiota, intestinal gene expression and serum metabolomic response via an integratedomic approach combining 16S rRNA gene sequencing, the OpenArray gene expression technology and 1 H-NMR spectroscopy. Fourteen piglets from diferent litters were sampled for blood, jejunum tissue and caecal content two days before (− 2d), and three days after (+3d) weaning. A clearly diferential ordination of caecal microbiota was observed. Higher abundances of Roseburia, Ruminococcus, Coprococcus, Dorea and Lachnospira genera in weaned piglets compared to prior to weaning showed the quick microbial changes of the piglets’ gut microbiota. Downregulation of OCLN, CLDN4, MUC2, MUC13, SLC15A1 and SLC13A1 genes, also evidenced the negative impact of weaning on gut barrier and digestive functions. Metabolomic approach pinpointed signifcant decreases in choline, LDL, triglycerides, fatty acids, alanine and isoleucine and increases in 3-hydroxybutyrate after weaning. Moreover, the correlation between microbiota and metabolome datasets revealed the existence of metabolic clusters interrelated to diferent bacterial clusters. Our results demonstrate the impact of weaning stress on the piglet and give insights regarding the associations between gut microbiota and the animal gene activity and metabolic response.info:eu-repo/semantics/publishedVersio