Ladderphane copolymers for high-temperature capacitive energy storage.

For capacitive energy storage at elevated temperatures1-4, dielectric polymers are required to integrate low electrical conduction with high thermal conductivity. The coexistence of these seemingly contradictory properties remains a persistent challenge for existing polymers. We describe here a class of ladderphane copolymers exhibiting more than one order of magnitude lower electrical conductivity than the existing polymers at high electric fields and elevated temperatures. Consequently, the ladderphane copolymer possesses a discharged energy density of 5.34 J cm-3 with a charge-discharge efficiency of 90% at 200 °C, outperforming the existing dielectric polymers and composites. The ladderphane copolymers self-assemble into highly ordered arrays by π-π stacking interactions5,6, thus giving rise to an intrinsic through-plane thermal conductivity of 1.96 ± 0.06 W m-1 K-1. The high thermal conductivity of the copolymer film permits efficient Joule heat dissipation and, accordingly, excellent cyclic stability at elevated temperatures and high electric fields. The demonstration of the breakdown self-healing ability of the copolymer further suggests the promise of the ladderphane structures for high-energy-density polymer capacitors operating under extreme conditions.

Strong tough hydrogels via the synergy of freeze-casting and salting out.

Natural load-bearing materials such as tendons have a high water content of about 70 per cent but are still strong and tough, even when used for over one million cycles per year, owing to the hierarchical assembly of anisotropic structures across multiple length scales1. Synthetic hydrogels have been created using methods such as electro-spinning2, extrusion3, compositing4,5, freeze-casting6,7, self-assembly8 and mechanical stretching9,10 for improved mechanical performance. However, in contrast to tendons, many hydrogels with the same high water content do not show high strength, toughness or fatigue resistance. Here we present a strategy to produce a multi-length-scale hierarchical hydrogel architecture using a freezing-assisted salting-out treatment. The produced poly(vinyl alcohol) hydrogels are highly anisotropic, comprising micrometre-scale honeycomb-like pore walls, which in turn comprise interconnected nanofibril meshes. These hydrogels have a water content of 70-95 per cent and properties that compare favourably to those of other tough hydrogels and even natural tendons; for example, an ultimate stress of 23.5 ± 2.7 megapascals, strain levels of 2,900 ± 450 per cent, toughness of 210 ± 13 megajoules per cubic metre, fracture energy of 170 ± 8 kilojoules per square metre and a fatigue threshold of 10.5 ± 1.3 kilojoules per square metre. The presented strategy is generalizable to other polymers, and could expand the applicability of structural hydrogels to conditions involving more demanding mechanical loading.

Ingenious Structure Engineering to Enhance Piezoelectricity in Poly(vinylidene fluoride) for Biomedical Applications.

The future development of wearable/implantable sensing and medical devices relies on substrates with excellent flexibility, stability, biocompatibility, and self-powered capabilities. Enhancing the energy efficiency and convenience is crucial, and converting external mechanical energy into electrical energy is a promising strategy for long-term advancement. Poly(vinylidene fluoride) (PVDF), known for its piezoelectricity, is an outstanding representative of an electroactive polymer. Ingeniously designed PVDF-based polymers have been fabricated as piezoelectric devices for various applications. Notably, the piezoelectric performance of PVDF-based platforms is determined by their structural characteristics at different scales. This Review highlights how researchers can strategically engineer structures on microscopic, mesoscopic, and macroscopic scales. We discuss advanced research on PVDF-based piezoelectric platforms with diverse structural designs in biomedical sensing, disease diagnosis, and treatment. Ultimately, we try to give perspectives for future development trends of PVDF-based piezoelectric platforms in biomedicine, providing valuable insights for further research.

Digital synthetic polymers for information storage.

Digital synthetic polymers with uniform chain lengths and defined monomer sequences have recently become intriguing alternatives to traditional silicon-based information devices or natural biomacromolecules for data storage. The structural diversity of information-containing macromolecules endows the digital synthetic polymers with higher stability and storage density but less occupied space. Through subtly designing each unit of coded structure, the information can be readily encoded into digital synthetic polymers in a more economical scheme and more decodable, opening up new avenues for molecular digital data storage with high-level security. This tutorial review summarizes recent advances in salient features of digital synthetic polymers for data storage, including encoding, decoding, editing, erasing, encrypting, and repairing. The current challenges and outlook are finally discussed to offer potential solution guidance and new perspectives for the creation of next-generation digital synthetic polymers and broaden the scope of their applicability.

In Situ Vaccination with An Injectable Nucleic Acid Hydrogel for Synergistic Cancer Immunotherapy.

Recently, therapeutic cancer vaccines have emerged as promising candidates for cancer immunotherapy. Nevertheless, their efficacies are frequently impeded by challenges including inadequate antigen encapsulation, insufficient immune activation, and immunosuppressive tumor microenvironment. Herein, we report a three-in-one hydrogel assembled by nucleic acids (NAs) that can serve as a vaccine to in situ trigger strong immune response against cancer. Through site-specifically grafting the chemodrug, 7-ethyl-10-hydroxycamptothecin (also known as SN38), onto three component phosphorothioate (PS) DNA strands, a Y-shaped motif (Y-motif) with sticky ends is self-assembled, at one terminus of which an unmethylated cytosine-phosphate-guanine (CpG) segment is introduced as an immune agonist. Thereafter, programmed cell death ligand-1 (PD-L1) siRNA that performs as immune checkpoint inhibitor is designed as a crosslinker to assemble with the CpG- and SN38-containing Y-motif, resulting in the formation of final NA hydrogel vaccine. With three functional agents inside, the hydrogel can remarkably induce the immunogenic cell death to enhance the antigen presentation, promoting the dendritic cell maturation and effector T lymphocyte infiltration, as well as relieving the immunosuppressive tumor environment. When inoculated twice at tumor sites, the vaccine demonstrates a substantial antitumor effect in melanoma mouse model, proving its potential as a general platform for synergistic cancer immunotherapy.

Asymmetric Synthesis of Chiral 1,2-Bis(Boronic) Esters Featuring Acyclic, Non-Adjacent 1,3-Stereocenters.

The construction of acyclic, non-adjacent 1,3-stereogenic centers, prevalent motifs in drugs and bioactive molecules, has been a long-standing synthetic challenge due to acyclic nucleophiles being distant from the chiral environment. In this study, we successfully synthesized highly valuable 1,2-bis(boronic) esters featuring acyclic and nonadjacent 1,3-stereocenters. Notably, this reaction selectively produces migratory coupling products rather than alternative deborylative allylation or direct allylation byproducts. This approach introduces a new activation mode for selective transformations of gem-diborylmethane in asymmetric catalysis. Additionally, we found that other gem-diborylalkanes, previously challenging due to steric hindrance, also successfully participated in this reaction. The incorporation of 1,2-bis(boryl)alkenes facilitated the diversification of the alkenyl and two boron moieties in our target compounds, thereby enabling access to a broad array of versatile molecules. DFT calculations were performed to elucidate the reaction mechanism and shed light on the factors responsible for the observed excellent enantioselectivity and diastereoselectivity. These were determined to arise from ligand-substrate steric repulsions in the syn-addition transition state.

Antifouling Asymmetric Block Copolymer Nanofilms via Freestanding Interfacial Polymerization for Efficient and Sustainable Water Purification.

Membrane materials that resist nonspecific or specific adsorption are urgently required in widespread practical applications, such as water purification, food processing, and life sciences. In water purification, inevitable membrane fouling not only limits membrane separation performance, leading to a decline in both permeance and selectivity, but also remarkably increases operation requirements, and augments extra maintenance costs and higher energy consumption. In this work, we report a freestanding interfacial polymerization (IP) fabrication strategy for in situ creation of asymmetric block copolymer (BCP) nanofilms with antifouling properties, greatly outperforming the conventional surface post-modification approaches. The resultant free-standing asymmetric BCP nanofilms with highly-dense, highly-hydrophilic polyethylene glycol (PEG) brushes on one side, can be readily formed via a typical IP process of a well-defined double-hydrophilic BCP composed of a highly-efficient antifouling PEG block and a membrane-forming multiamine block. The asymmetric BCP nanofilms have been applied for efficient and sustainable natural water purification, demonstrating extraordinary antifouling capabilities accompanied with superior separation performance far beyond commercial polyamide nanofiltration membranes. The antifouling behaviors of asymmetric BCP nanofilms derived from the combined effect of the hydration layer, electrostatic repulsion and steric hindrance were further elucidated by water flux and fouling resistance in combination with all-atom molecular dynamics (MD) simulation. This work opens up a new avenue for the large-scale and low-cost creation of broad-spectrum, asymmetric membrane materials with diverse functional "defect-free" surfaces in real-world applications.

Surface Chain-Transfer Ring-Opening Metathesis Polymerization.

Ring-opening metathesis polymerization (ROMP) is a powerful method to graft various types of polymer chains to a given surface. While surface-initiated ROMP (SI-ROMP) serves as an efficient tool for surface modification and is therefore widely reported, the method requires grafting (1) the olefin substrate and (2) the metathesis catalyst to the surface prior to the polymerization with multiple synthetic and work up steps. To overcome this difficulty, we proposed the use of the chain-transfer reaction as an alternative method for surface modification. Terminal olefins are grafted to the surface without the need to graft the metathesis catalysts, and polymers with olefin backbones are polymerized and grafted simultaneously via both ROMP and chain transfer (cross-metathesis between olefins from backbones and surfaces). Compared to SI-ROMP, this surface-chain transfer ROMP (SC-ROMP) method avoids grafting the catalyst and growing polymer chains from the surface and could be achieved in a single step. Various types of surfaces like carbon nanotubes, carbon fibers, graphene nanosheets, and silica microspheres are used for demonstration. We envision that this work could bring a convenient and effective solution to surface modification via ROMP.

Facile, Controllable, and Ultrathin NiFe-LDH In Situ Grown on a Ni Foam by Ultrasonic Self-Etching for Highly Efficient Urine Conversion.

As the primary source of nitrogen pollutants in domestic sewage, urine is also an alternative for H2 production via electrochemical processes. However, it suffers from sluggish kinetics and noble-metal catalyst requirement. Here, we report a non-precious ultrathin NiFe-layered double hydroxide catalyst for the remarkable conversion of urea into N2 and H2, which is in situ grown on a Ni foam via ultrasonic self-etching in Fe3+/ethylene glycol (EG). EG regulates the etching rate of Fe3+, resulting in an ultrathin nanosheet structure with the aid of ultrasonication. This structure dramatically promotes the dehydrogenation process via decreasing the nanolayer thickness from 120 to 3.4 nm and leads to a 4.8-fold increase in the generation of active sites. It exhibits record urea oxidation kinetics (390.8 mA·cm-2 at 1.5 V vs RHE) with excellent stability (120 h), which is 11.8 times better than that of commercial Pt/C catalyst (33.1 mA·cm-2). Tests with real urine at 20 mA cm-2 achieve 74% total nitrogen removal and 2853 µmol·h-1 of H2 production. This study provides an attractive landscape for producing H2 by consuming urine biowastes.

Superhydrophobic photothermal icephobic surfaces based on candle soot.

Ice accumulation causes various problems in our daily life for human society. The daunting challenges in ice prevention and removal call for novel efficient antiicing strategies. Recently, photothermal materials have gained attention for creating icephobic surfaces owing to their merits of energy conservation and environmental friendliness. However, it is always challenging to get an ideal photothermal material which is cheap, easily fabricating, and highly photothermally efficient. Here, we demonstrate a low-cost, high-efficiency superhydrophobic photothermal surface, uniquely based on inexpensive commonly seen candle soot. It consists of three components: candle soot, silica shell, and polydimethylsiloxane (PDMS) brushes. The candle soot provides hierarchical nano/microstructures and photothermal ability, the silica shell strengthens the hierarchical candle soot, and the grafted low-surface-energy PDMS brushes endow the surface with superhydrophobicity. Upon illumination under 1 sun, the surface temperature can increase by 53 °C, so that no ice can form at an environmental temperature as low as -50 °C and it can also rapidly melt the accumulated frost and ice in 300 s. The superhydrophobicity enables the melted water to slide away immediately, leaving a clean and dry surface. The surface can also self-clean, which further enhances its effectiveness by removing dust and other contaminants which absorb and scatter sunlight. In addition, after oxygen plasma treatment, the surface can restore superhydrophobicity with sunlight illumination. The presented icephobic surface shows great potential and broad impacts owing to its inexpensive component materials, simplicity, ecofriendliness, and high energy efficiency.