Exploration of high‐performance cathode materials for rechargeable aqueous Zn ion batteries (ZIBs) is highly desirable. The potential of molybdenum trioxide (MoO
3
) in other electrochemical energy storage devices has been revealed but held understudied in ZIBs. Herein, a demonstration of orthorhombic MoO
3
as an ultrahigh‐capacity cathode material in ZIBs is presented. The energy storage mechanism of the MoO
3
nanowires based on Zn
2+
intercalation/deintercalation and its electrochemical instability mechanism are particularly investigated and elucidated. The severe capacity decay of the MoO
3
nanowires during charging/discharging cycles arises from the dissolution and the structural collapse of MoO
3
in aqueous electrolyte. To this end, an effective strategy to stabilize MoO
3
nanowires by using a quasi‐solid‐state poly(vinyl alcohol)(PVA)/ZnCl
2
gel electrolyte to replace the aqueous electrolyte is developed. The capacity retention of the assembled ZIBs after 400 charge/discharge cycles at 6.0 A g
−1
is significantly boosted, from 27.1% (in aqueous electrolyte) to 70.4% (in gel electrolyte). More remarkably, the stabilized quasi‐solid‐state ZIBs achieve an attracting areal capacity of 2.65 mAh cm
−2
and a gravimetric capacity of 241.3 mAh g
−1
at 0.4 A g
−1
, outperforming most of recently reported ZIBs.
The activation of the α-carbons of carboxylic esters and related carbonyl compounds to generate enolate equivalents as nucleophiles is one of the most powerful strategies in organic synthesis. We reasoned that the horizons of chemical synthesis could be greatly expanded if the typically inert β-carbons of saturated esters could be used as nucleophiles. However, despite the rather significant fundamental and practical values, direct use of the β-carbons of saturated carbonyl compounds as nucleophiles remains elusive. Here we report the catalytic activation of simple saturated ester β-carbons as nucleophiles (β-carbon activation) using N-heterocyclic carbene organocatalysts. The catalytically generated nucleophilic β-carbons undergo enantioselective reactions with electrophiles such as enones and imines. Given the proven rich chemistry of ester α-carbons, we expect this catalytic activation mode for saturated ester β-carbons to open a valuable new arena for new and useful reactions and synthetic strategies.
INPP5K (SKIP) is an inositol 5-phosphatase that localizes in part to the endoplasmic reticulum (ER). We show that recruitment of INPP5K to the ER is mediated by ARL6IP1, which shares features of ER-shaping proteins. Like ARL6IP1, INPP5K is preferentially localized in ER tubules and enriched, relative to other ER resident proteins (Sec61β, VAPB, and Sac1), in newly formed tubules that grow along microtubule tracks. Depletion of either INPP5K or ARL6IP1 results in the increase of ER sheets. In a convergent but independent study, a screen for mutations affecting the distribution of the ER network in dendrites of the PVD neurons of led to the isolation of mutants in CIL-1, which encodes the INPP5K worm orthologue. The mutant phenotype was rescued by expression of wild type, but not of catalytically inactive CIL-1. Our results reveal an unexpected role of an ER localized polyphosphoinositide phosphatase in the fine control of ER network organization.
An N-heterocyclic carbene (NHC) catalyzed domino reaction triggered by a δ-LUMO activation of α,β-γ,δ-diunsaturated enal has been developed for the formal [4 + 2] construction of multisubstituted arenes and 3-ylidenephthalide. These two products, formed in a highly chemo- and regioselective manner, were obtained via different catalytic pathways due to a simple change of the substrate. The activation of the remote δ-carbon of unsaturated aldehydes expands the synthetic potentials of NHC organocatalysis.
Atroposelective arene formation is an efficient method to build axially chiral molecules with multi‐substituted arenes. Reported here is an organocatalyzed atroposelective arene formation reaction by an N‐heterocyclic carbene (NHC) catalyzed formal [4+2] cycloaddition of conjugated dienals and α‐aryl ketones. This study expands the synthetic potential of NHC organocatalysis and provides a competitive pathway for the synthesis of axially chiral ligands, catalysts, and other functional molecules.
Our previous work showed that the cell adhesion molecule SAX-7 forms an elaborate pattern in epidermal cells, which instructs PVD dendrite branching. However, the molecular mechanism forming the SAX-7 pattern in the epidermis is not fully understood. Here, we report that the dynein light intermediate chain DLI-1 and the fusogen EFF-1 are required in epidermal cells to pattern SAX-7. While previous reports suggest that these two molecules act cell-autonomously in the PVD, our results show that the disorganized PVD dendritic arbors in these mutants are due to the abnormal SAX-7 localization patterns in epidermal cells. Three lines of evidence support this notion. First, the epidermal SAX-7 pattern was severely affected in and mutants. Second, the abnormal SAX-7 pattern was predictive of the ectopic PVD dendrites. Third, expression of DLI-1 or EFF-1 in the epidermis rescued both the SAX-7 pattern and the disorganized PVD dendrite phenotypes, whereas expression of these molecules in the PVD did not. We also show that DLI-1 functions cell-autonomously in the PVD to promote distal branch formation. These results demonstrate the unexpected roles of DLI-1 and EFF-1 in the epidermis in the control of PVD dendrite morphogenesis.
A chemo- and enantioselective cross-aza-benzoin reaction between enals and isatin-derived ketimines is disclosed. The high chemoselectivity (of the acyl anion reaction over enal α- and β-carbon reactions) is enabled by the electronic and steric properties of the N-heterocyclic carbene organocatalyst.
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