Reversible covalent polymers are able to change their bond arrangement and structure via reversible reaction triggered by external stimuli including heating, light and pH, while retaining the ...stability of irreversible covalent polymers in the absence of the stimuli. In recent years, more and more research has been devoted to utilization of reversible covalent bonds in synthesizing new materials, which not only overcomes disadvantages of permanent covalent polymers, but also brings in new functionalities. More importantly, a series of novel techniques dedicated to polymerized products with features such as properties regulation, self-healing, reprocessing, solid state recycling, and controllable degradation are developed, heralding the opportunity of upgrading of traditional polymer engineering. Although the exploration of this emerging topic is still in its infancy, the advances so far are encouraging and clearly directed to large scale applications. This review systematically outlines this promising trend, following a bottom-up strategy, taking into account both theoretical and experimental achievements. It mainly consists of four parts, involving design and preparation: (i) the basis of reversible covalent chemistry, (ii) rheology of reversible covalent polymers, (iii) methods of construction of reversible covalent polymers, and (iv) smart, adaptive properties offered by reversible covalent chemistry. The key elements for realizing reorganization of polymers containing reversible covalent bonds are covered. The advantages and weaknesses of representative reaction systems are analyzed, while the challenges and opportunities to engineering application of the equilibrium control based on reversible covalent chemistry for producing end-use polymers are summarized. In this way, the readers may grasp both the overall situation as well as insight into future work.
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.
Parkinson's disease (PD) is a neurodegenerative disorder characterized by the gradual loss of midbrain dopaminergic neurons in association with aggregation of α-synuclein. Oxidative damage has been ...widely implicated in this disease, though the mechanisms involved remain elusive. Here, we demonstrated that preferential accumulation of peroxidized phospholipids and loss of the antioxidant enzyme glutathione peroxidase 4 (GPX4) were responsible for vulnerability of midbrain dopaminergic neurons and progressive motor dysfunctions in a mouse model of PD. We also established a mechanism wherein iron-induced dopamine oxidation modified GPX4, thereby rendering it amenable to degradation via the ubiquitin-proteasome pathway. In conclusion, this study unraveled what we believe to be a novel pathway for dopaminergic neuron degeneration during PD pathogenesis, driven by dopamine-induced loss of antioxidant GPX4 activity.
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.
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.
The exotic topological surface states of Dirac or Weyl semimetals, namely Fermi arcs, are predicted to be spin polarized, while their spin polarization nature is still not revealed by transport ...measurements. Here, we report the spin-polarized transport in a Dirac semimetal Cd_{3}As_{2} nanowire employing the ferromagnetic electrodes for spin detection. The spin-up and spin-down states can be changed by reversing the current polarity, showing the spin-momentum locking property. Moreover, the nonlocal measurements show a high fidelity of the spin signals, indicating the topological protection nature of the spin transport. As tuning the Fermi level away from the Dirac point by gate voltages, the spin signals gradually decrease and finally are turned off, which is consistent with the fact that the Fermi arc surface state has the maximum ratio near the Dirac point and disappears above the Lifshitz transition point. Our results should be valuable for revealing the transport properties of the spin-polarized Fermi arc surface states in topological semimetals.
To provide self-healing ability to polyurethane elastomer, alkoxyamine-based diol was synthesized and reacted with tri-functional homopolymer of hexamethylene diisocyanate (tri-HDI) and polyethylene ...glycol (PEG). Because alkoxyamines acted as crosslinkers of the resultant polyurethane, the thermally reversible fission/recombination of C–ON bonds in alkoxyamine moieties enabled repeated crosslinking and de-crosslinking of polyurethane chains at certain temperature and hence crack healing. Both qualitative and quantitative characterizations demonstrated that the reversibly crosslinked polyurethane was capable of re-bonding ruptured parts and restoring mechanical strength. The remendability was a function of molecular structure and compositions of the components, which can be purposely tuned according to different application demands.
Display omitted
A crosslinked silicone elastomer is prepared by utilizing polydimethylsiloxane as the host material and disulfide bond-containing silane as the crosslinking agent. By taking advantage of the sunlight ...activated metathesis of the included disulfide bonds, the crosslinked silicone elastomer can be self-healed and recycled for multiple times without any catalyst under sunshine. A series of verification experiments are carried out to reveal the underlying mechanism and the dynamicity of the silicone. Because the key raw materials are commercially available and the manufacturing follows common industrial procedures, the outcomes of this proof-of-concept study may be easily applied in practice. The simple and eco-friendly method would help to increase reliability and durability of silicone products and minimize wasting of resources.
Display omitted
•Crosslinked polydimethylsiloxane exhibits sunlight induced dynamicity.•Catalyst-free disulfide metathesis in silicone elastomer is activated by sunlight.•Silicone elastomer can be repeatedly self-healed and recycled under sunshine.
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.
Traditional interpenetrating polymer networks (IPNs) are not adaptable materials because the topological structure of the macromolecules cannot be changed, which limits their structural ...rearrangement, reprocessing, and recycling. Here in this work we present a strategy for preparing reversibly interlocking networks (RILNs) from two preformed immiscible polymer networks based on dynamic covalent chemistry. The frequently opening and closing of the single networks enabled by the exchange reactions of the embedded orthogonal dynamic covalent bonds and stronger intercomponent interaction mainly account for the formation of the interlocking topology architecture of the RILNs. The resultant RILNs are rather homogeneous, which not only possess stimulus-responsive adaptive performance like self-healing but also exhibit nonlinear improvement in static and dynamic mechanical properties. By taking advantage of the reversible bonding, more importantly, the RILNs can be unlocked reproducing the pristine single networks, and the relocking/unlocking cycling is allowed to proceed for multiple times, which are not available for IPNs as defined by their chemical nature. It is anticipated that the proposed methodology provides a new idea for producing multifunctional cross-linked polymers capable of repeated controlled degradation and regeneration.
PDF
