As one of the fascinating high capacity cathodes, O3‐type layered oxides usually suffer from their intrinsic air sensitivity and sluggish kinetics originating from the spontaneous lattice Na ...extraction during air exposure and high tetrahedral site energy of Na+ diffusion transition state. What is worse, the improvement on the two handicaps is hard to simultaneously realize because of the contradiction between Na containment suggested in air stability mechanism and enhanced Na diffusion mentioned in kinetics strategy. Herein, it is shown that a simple strategy of introducing proper Na vacancies into lattice can simultaneously realize a dual performance improvement. Na vacancies decrease the charge density on transitional metal ions and enhance the antioxidative capability of material, ensuring a stable lattice Na containment for Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2 when exposed to air. Additionally, more Na+ diffusional sites and enlarged Na layer spacing are obtained and result in a significantly decreased energy barrier from ≈1000 to 300 meV and a high rate capability of 70.8% retention at 2000 mA g−1. Remarkably, such a strategy can be easily realized by either pre‐ or post‐treating, which exhibits excellent universality for various O3 materials, implying its enormous potential to promote the commercial application of O3‐type cathodes.
A universal strategy of introducing proper Na vacancies into a crystal lattice is proposed to simultaneously improve air‐stability and kinetics of O3‐type layered oxide cathodes. The dual improvement benefits from the multiple effects of Na vacancies on crystalline and electronic structure, namely, decreased charge density on transition metal ions, enhanced antioxidative capability, decreased Na+ diffusion barrier, and optimized migration path.
Pyroptosis is a form of cell death mediated by gasdermin D (GSDMD); it is characterised by NLRP3 inflammasome activation, caspase activation, cell membrane pore formation, and the release of ...interleukin-1β and interleukin-18. NLRP3 inflammasome activation plays a central role in pyroptosis. Recent research has suggested that NLRP3 inflammasome activation may be involved in the occurrence and development of diabetes mellitus and its associated complications. This finding provided the impetus for us to clarify the significance of pyroptosis in diabetes. In this review, we summarise the current understanding of the molecular mechanisms involved in pyroptosis, as well as recent advances in the role of NLRP3 inflammasome activation and pyroptosis in the development of diabetes and diabetic complications.
The activation mechanisms of NLRP3 inflammasome. Display omitted
The first highly diastereo‐ and enantioselective multicomponent reaction of diazooxindoles, nitrosoarenes, and nitroalkenes using a newly developed hydrogen‐bond catalyst has been successfully ...developed for the efficient construction of a series of spirooxindole derivatives with excellent functional‐group tolerance. Spirooxindoles are formed in excellent yields and stereoselectivities, and the method represents an unprecedented approach for trapping the active intermediate with a nitroalkene to form biologically important compounds having three contiguous stereogenic centers with excellent asymmetric induction.
Multiple players: The first highly stereoselective multicomponent reaction of diazooxindoles, nitrosoarenes, and nitroalkenes with a newly developed hydrogen‐bond catalyst has been successfully developed. The spirooxindole products are isolated in excellent yields and stereoselectivities, and contain three contiguous stereogenic centers. R′′′=aryl or alkyl.
Metastasis causes the vast majority of colorectal carcinoma (CRC)-related deaths. However, little is known about the specific traits and underlying mechanisms of metastasis-initiating cells in ...primary CRC. And whether or not circular RNAs (circRNAs) take part in this particular event remain not adequately stated yet.
A screening method based on Transwell assay was first applied to build CRC subgroups with different metastatic potential. High throughput RNA sequencing was used to find out novel metastatic drivers in CRC metastasis-initiating step. A series of in vitro and in vivo assays were further applied to elucidate the functions and underlying molecular mechanisms of circRNAs in CRC metastasis.
A circRNA consisting of exon 8-11 of LONP2, termed as circLONP2, was upregulated in metastasis-initiating CRC subgroups. Aberrant higher expression of circLONP2 was observed in primary CRC tissues with established metastasis, and along the invasive margin in metastatic site. High expression of circLONP2 predicted unfavorable overall survival. Functional studies revealed that circLONP2 could enhance the invasiveness of CRC cells in vitro, and targeting circLONP2 through anti-sense oligonucleotide (ASO) dramatically reduced the penetrance of metastasis to foreign organs in vivo. Mechanically, circLONP2 directly interacted with and promoted the processing of primary microRNA-17 (pri-miR-17), through recruiting DiGeorge syndrome critical region gene 8 (DGCR8) and Drosha complex in DDX1-dependent manner. Meanwhile, upregulated mature miR-17-5p could be assembled into exosomes and internalized by neighboring cells to enhance their aggressiveness.
Our data indicate that circLONP2 acts as key metastasis-initiating molecule during CRC progression through modulating the intracellular maturation and intercellular transfer of miR-17, resulting in dissemination of metastasis-initiating ability in primary site and acceleration of metastasis formation in foreign organs. circLONP2 could serve as an effective prognostic predictor and/or novel anti-metastasis therapeutic target in CRC treatment.
Age‐associated obesity and muscle atrophy (sarcopenia) are intimately connected and are reciprocally regulated by adipose tissue and skeletal muscle dysfunction. During ageing, adipose inflammation ...leads to the redistribution of fat to the intra‐abdominal area (visceral fat) and fatty infiltrations in skeletal muscles, resulting in decreased overall strength and functionality. Lipids and their derivatives accumulate both within and between muscle cells, inducing mitochondrial dysfunction, disturbing β‐oxidation of fatty acids, and enhancing reactive oxygen species (ROS) production, leading to lipotoxicity and insulin resistance, as well as enhanced secretion of some pro‐inflammatory cytokines. In turn, these muscle‐secreted cytokines may exacerbate adipose tissue atrophy, support chronic low‐grade inflammation, and establish a vicious cycle of local hyperlipidaemia, insulin resistance, and inflammation that spreads systemically, thus promoting the development of sarcopenic obesity (SO). We call this the metabaging cycle. Patients with SO show an increased risk of systemic insulin resistance, systemic inflammation, associated chronic diseases, and the subsequent progression to full‐blown sarcopenia and even cachexia. Meanwhile in many cardiometabolic diseases, the ostensibly protective effect of obesity in extremely elderly subjects, also known as the ‘obesity paradox’, could possibly be explained by our theory that many elderly subjects with normal body mass index might actually harbour SO to various degrees, before it progresses to full‐blown severe sarcopenia. Our review outlines current knowledge concerning the possible chain of causation between sarcopenia and obesity, proposes a solution to the obesity paradox, and the role of fat mass in ageing.
This article addresses the finite-time event-triggered adaptive neural control for fractional-order nonlinear systems. Based on the backstepping technique, a novel adaptive event-triggered control ...scheme is proposed, and finite-time stability criteria are introduced with the aim to ensure that the tracking error enters into a small region around the origin in finite time. Finally, the stability of the closed-loop system is ensured via a fractional Lyapunov function theory and two simulation examples were used to prove the validity of the designed control scheme.
Although great success has been achieved in asymmetric fluoroalkylation reactions via nucleophilic or electrophilic processes, the development of asymmetric radical versions of this type of reactions ...remains a formidable challenge because of the involvement of highly reactive radical species. Here we report a catalytic asymmetric radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes with commercially available fluoroalkylsulfonyl chlorides as the radical sources, providing a versatile platform to access four types of enantioenriched α-tertiary pyrrolidines bearing β-perfluorobutanyl, trifluoromethyl, difluoroacetyl and even difluoromethyl groups in excellent yields and with excellent enantioselectivity. The key to success is not only the introduction of the CuBr/chiral phosphoric acid dual-catalytic system but also the use of silver carbonate to suppress strong background and side hydroamination reactions caused by a stoichiometric amount of the in situ generated HCl. Broad substrate scope, excellent functional group tolerance and versatile functionalization of the products make this approach very practical and attractive.
The problem of finite-time adaptive tracking control against event-trigger error is investigated in this article for a type of uncertain nonlinear systems. By fusing the techniques of command filter ...backstepping technical and event-triggered control (ETC), an adaptive event-triggered design method is proposed to construct the controller, under which the effect of event-triggered error can be compensated completely. Moreover, the proposed controller can increase robustness against uncertainties and event error in the backstepping design framework. In particular, we establish the finite-time convergence condition under which the tracking error asymptotically converges to zero in finite time with the aid of a scaling function. Detailed and rigorous stability proofs are given by making use of the improved finite time stability criterion. Two simulation examples are provided to exhibit the validity of the designed adaptive ETC approach.
Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by ...1,2‐boron shift have remained to be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled by 1,2‐boron shift was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of allylic carbonates at the elevated temperature. Notably, the highly valuable (bis‐boryl)alkenes have enabled an array of diversifications to access versatile molecules. Extensive experimental and computational studies were conducted to elucidate the reaction mechanism of DKR process and clarify the origin of excellent enantioselectivities.
We have developed an Ir‐catalyzed asymmetric allylic alkylation via 1,2‐boron shift to access enantioenriched gem‐diborylalkenes. In this reaction, excellent enantioselectivities were obtained by simply improving the reaction temperature via an impressive DKR process. DFT calculations and extensive mechanistic studies were conducted to elucidate the reaction mechanism and the origin of excellent enantioselectivities.
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