Stimuli‐responsive polymers built by reversible covalent bonds used to possess unbalanced mechanical properties. Here, a crosslinked polyurethane containing aromatic pinacol as a novel reversible CC ...bond provider is synthesized, whose tensile strength and failure strain are tunable from 27.3 MPa to as high as 115.2 MPa and from 324% to 1501%, respectively, owing to the relatively high bond energy of the CC bond of pinacol as well as the hydrogen bond between hard segments and semicrystalline soft segments. Moreover, the dynamic equilibrium of pinacol enables self‐healing and recycling of the polymer. Interestingly, the dynamic exchange among macromolecules, for the first time, successfully cooperates with solid‐state drawing that applies to thermoplastics, realizing strengthening of thermoset. Meanwhile, the radicals derived from homolysis of pinacol can repeatedly initiate polymerization of vinyl monomers. The fruitful outcomes of this work may create a series of promising new techniques.
The CC bond of pinacol is dynamically reversible at moderate temperature. A crosslinked polyurethane carrying pinacol unit is synthesized, which can be self‐healed, reprocessed, and recycled via the catalyst‐free reversible homolysis/radicals recombination of the CC bond. Moreover, its strength can be greatly improved by solid‐state drawing. The radicals created during homolysis are enabled to repeatedly initiate polymerization of vinyl monomers.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Ultrafast‐response (20 μs) UV detectors, which are visible‐blind and self‐powered, in devices where an n‐type ZnO nanowire partially lies on a p‐type GaN film, are demonstrated. Moreover, a ...CdSe‐nanowire red‐light detector powered by a nanoscale ZnO/GaN photovoltaic cell is also demonstrated, which extends the device function to a selective multiwavelength photodetector and shows the function of an optical logical AND gate.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Dielectric capacitors are fundamental energy storage components in electronics and electric power systems due to their unique ultrahigh power density. However, their relatively low energy storage ...density is a long‐standing challenge which greatly limits their practical application range. Chitosan (CS) and montmorillonite (MMT) are two kinds of materials that exist abundantly on the earth with natural surface charges. The positively charged CS and negatively charged MMT can be self‐assembled into the typical sandwich‐structured CS/MMT/CS 2D structure through an electrostatic attraction. Loading these surface‐charged sandwich‐structured nanosheets into poly(vinylidene fluoride)‐based composite with a weight fraction as tiny as 0.3 wt.%, an ultrahigh energy storage density of 32.5 J cm−3 accompanied with a high efficiency of 64% are concurrently achieved with a very low cost and scalable process. Guided by finite element simulation, it is revealed that a number of electric potential wells that exist in the charged sandwich nanosheets impede the acceleration of internal charges and hinder the growth of electrical trees. The results offer a novel paradigm for exploring ultrahigh energy storage density capacitors in an economical way.
The reported chitosan/montmorillonite/chitosan (CMC) nanosheets are self‐assembled via electrostatic attraction. The electric potential wells formed in charged CMC nanosheets can significantly improve the breakdown strength and the energy storage properties of poly (vinylidene fluoride)‐based composite dielectrics.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Endonuclease G (ENDOG), a mitochondrial nuclease, is known to participate in many cellular processes, including apoptosis and paternal mitochondrial elimination, while its role in autophagy remains ...unclear. Here, we report that ENDOG released from mitochondria promotes autophagy during starvation, which we find to be evolutionally conserved across species by performing experiments in human cell lines, mice, Drosophila and C. elegans. Under starvation, Glycogen synthase kinase 3 beta-mediated phosphorylation of ENDOG at Thr-128 and Ser-288 enhances its interaction with 14-3-3γ, which leads to the release of Tuberin (TSC2) and Phosphatidylinositol 3-kinase catalytic subunit type 3 (Vps34) from 14-3-3γ, followed by mTOR pathway suppression and autophagy initiation. Alternatively, ENDOG activates DNA damage response and triggers autophagy through its endonuclease activity. Our results demonstrate that ENDOG is a crucial regulator of autophagy, manifested by phosphorylation-mediated interaction with 14-3-3γ, and its endonuclease activity-mediated DNA damage response.
Inspired by naturally occurring species that allow for self-healing of nonfatal harm, self-healing polymeric materials have been prepared and represent a component of the intelligent materials ...family. These materials possess the inherent ability to rehabilitate damage produced during manufacturing and/or usage. The self-healing methodologies developed to date can be classified as intrinsic or extrinsic according to the method used to deliver the healing components to the target site in the material. Intrinsic self-healing operates through inter- or intra-macromolecular interactions, whereas extrinsic self-healing makes use of a pre-embedded healing agent. Extrinsic self-healing can be more easily realized in commercially available polymers because no structural modification of the matrix molecules is required. In recent years, extrinsic self-healing based on microencapsulated healing agents has attracted growing interest. Extrinsic self-healing in a variety of materials (including thermosets, thermoplastics, rigid, and elastomeric materials) has been demonstrated and offers recovery of both mechanical and non-structural functional properties. Self-healing based on microcapsules can deliver further results if combined with intrinsic self-healing. Using a bottom-up perspective, the current article presents a comprehensive review of recent progress in this field from the viewpoint of material design and preparation. The topics presented include (i) a basic overview of self-healing systems, (ii) microencapsulation techniques (e.g., in situ polymerization, interfacial polymerization, Pickering emulsion templating, miniemulsion polymerization, solvent evaporation/solvent extraction, sol–gel reaction, etc.), (iii) crack response of microcapsules, and (iv) healing chemistries (e.g., ring-opening metathesis polymerization, polycondensation, anionic ring opening polymerization, cationic polymerization, free radical polymerization, addition reaction, etc.). The strengths and weaknesses of each microencapsulation technique and type of healing chemistry are analyzed and compared. Additionally, formulation optimization (including species of healing agent and wall substance of capsules), processing, structure and property relationship, healing mechanisms, and stability are discussed. Trends and challenges are summarized at the end of the review. The scope of this review is to provide the reader with an overview of achievements to date and insight into future development for engineering applications.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Advances in targeted covalent inhibitors (TCIs) have been made by using lysine‐reactive chemistries. Few aminophiles possessing balanced reactivity/stability for the development of cell‐active TCIs ...are however available. We report herein lysine‐reactive activity‐based probes (ABPs; 2–14) based on the chemistry of aryl fluorosulfates (ArOSO2F) capable of global reactivity profiling of the catalytic lysine in human kinome from mammalian cells. We concurrently developed reversible covalent ABPs (15/16) by installing salicylaldehydes (SA) onto a promiscuous kinase‐binding scaffold. The stability and amine reactivity of these probes exhibited a broad range of tunability. X‐ray crystallography and mass spectrometry (MS) confirmed the successful covalent engagement between ArOSO2F on 9 and the catalytic lysine of SRC kinase. Chemoproteomic studies enabled the profiling of >300 endogenous kinases, thus providing a global landscape of ligandable catalytic lysines of the kinome. By further introducing these aminophiles into VX‐680 (a noncovalent inhibitor of AURKA kinase), we generated novel lysine‐reactive TCIs that exhibited excellent in vitro potency and reasonable cellular activities with prolonged residence time. Our work serves as a general guide for the development of lysine‐reactive ArOSO2F‐based TCIs.
Lysine‐reactive activity‐based probes based on aryl fluorosulfates (ArOSO2F) are reported, enabling successful profiling of >300 endogenous kinases and providing a global landscape of ligandable catalytic lysines of the human kinome. Introduction of these aminophiles into a noncovalent Aurora A kinase inhibitor led to novel lysine‐reactive inhibitors that exhibited excellent in vitro potency and cellular activities with prolonged residence time.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Caffeine is a major component of xanthine alkaloids and commonly consumed in many popular beverages. Due to its occasional side effects, reduction of caffeine in a natural way is of great importance ...and economic significance. Recent studies reveal that caffeine can be converted into non-stimulatory theacrine in the rare tea plant Camellia assamica var. kucha (Kucha), which involves oxidation at the C8 and methylation at the N9 positions of caffeine. However, the underlying molecular mechanism remains unclear. Here, we identify the theacrine synthase CkTcS from Kucha, which possesses novel N9-methyltransferase activity using 1,3,7-trimethyluric acid but not caffeine as a substrate, confirming that C8 oxidation takes place prior to N9-methylation. The crystal structure of the CkTcS complex reveals the key residues that are required for the N9-methylation, providing insights into how caffeine N-methyltransferases in tea plants have evolved to catalyze regioselective N-methylation through fine tuning of their active sites. These results may guide the future development of decaffeinated drinks.
A pandemic of severe acute respiratory syndrome coronavirus‐2 (SARS‐CoV‐2) infection broke out all over the world; however, epidemiological data and viral shedding in pediatric patients are limited. ...We conducted a retrospective, multicenter study, and followed‐up with all children from the families with SARS‐CoV‐2 infected members in Zhejiang Province, China. All infections were confirmed by testing the SARS‐CoV‐2 RNA with real‐time reverse transcription PCR method, and epidemiological data between children and adults in the same families were compared. Effect of antiviral therapy was evaluated observationally and fecal‐viral excretion times among groups with different antiviral regiments were compared with Kaplan‐Meier plot. By 29 February 2020, 1298 cases from 883 families were confirmed with SARS‐CoV‐2 infection and 314 of which were families with children. Incidence of infection in child close contacts was significantly lower than that in adult contacts (13.2% vs 21.2%). The mean age of 43 pediatric cases was 8.2 years and mean incubation period was 9.1 days. Forty (93.0%) were family clustering. Thirty‐three children had coronavirus disease 2019 (20 pneumonia) with mild symptoms and 10 were asymptomatic. Fecal SARS‐CoV‐2 RNA detection was positive in 91.4% (32/35) cases and some children had viral excretion time over 70 days. Viral clearance time was not different among the groups treated with different antiviral regiments. No subsequent infection was observed in family contacts of fecal‐viral‐excreting children. Children have lower susceptibility of SARS‐CoV‐2 infection, longer incubation, and fecal‐viral excretion time. Positive results of fecal SARS‐CoV‐2 RNA detection were not used as indication for hospitalization or quarantine.
Highlights
Children had lower susceptibility for SARS‐CoV‐2 infection than adults.
Children had longer incubation period and fecal viral excretion time after infected by SARS‐CoV‐2.
Viral clearance time was not different among the groups treated with different antiviral regiments.
Children had milder clinical symptoms, better clinical outcome, and more common fecal viral excretion.
Positive results of fecal SARS‐CoV‐2 RNA detection are not used as indication for hospitalization or quarantine.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The recent outbreak of Zika virus (ZIKV) has imposed a serious threat to public health. Here we report the crystal structure of the ZIKV NS5 protein in complex with S-adenosyl-L-homocysteine, in ...which the tandem methyltransferase (MTase) and RNA-dependent RNA polymerase (RdRp) domains stack into one of the two alternative conformations of flavivirus NS5 proteins. The activity of this NS5 protein is verified through a de novo RdRp assay on a subgenomic ZIKV RNA template. Importantly, our structural analysis leads to the identification of a potential drug-binding site of ZIKV NS5, which might facilitate the development of novel antivirals for ZIKV.
To impart self-healing polymers largely adjustable dynamicity and mechanical performance, here we develop libraries of catalyst-free reversible polythioureas directly from commodity 1,4-phenylene ...diisothiocyanate and amines via facile click chemistry based modular assembly. By using the amine modules with various steric hindrances and flexibilities, the reversible thiourea units acquire triggering temperatures from room temperature to 120 °C. Accordingly, the derived self-healable, recyclable and controlled degradable dynamically crosslinked polythioureas can take effect within wide temperature range. Moreover, mechanical properties of the materials can be tuned covering plastics, elastomers and fibers using (i) different assemble modules or (ii) solid-state stretching. Particularly, unidirectional stretching leads to the record-high tensile strength of 266 MPa, while bidirectional stretching provides the materials with biaxial strengths up to over 120 MPa. The molecular mechanism and technological innovations discussed in this work may benefit promotion and application of self-healing polymers towards greatly diverse demands and scenarios.
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