Solid polymer electrolytes (SPEs) synthesized via in-situ polymerization exhibit excellent interfacial compatibility; however their inherently low ionic conductivity limits their application in solid-state lithium (Li) metal batteries (LMBs). Herein, we report a type of SPE composed of succinonitrile (SN), LiTFSI, and cross-linked polymer matrix (SNCE). Within the electrolyte, Li+ coordinates with ether, carbonyl, and nitrile groups; the strong SN-Li+ interactions promote Li+ detachment from the polymer matrix, forming continuous Li+ conduction pathways. This design imparts both mechanical robustness and superior electrochemical performance to the SPEs. The cross-linked structure restricts the migration of SN, suppressing undesirable side reactions with the Li anode at the initial stage, compensating for the reduction in mechanical strength due to SN addition, and further improving electrochemical stability. The optimized SNCE-2 exhibits an ionic conductivity of 0.16 mS cm-1 at 30 degrees C, an electrochemical stability window (ESW) up to 5.2 V, and a Li+ transference number (tLi+) of 0.44. The in-situ polymerization ensures intimate electrode-electrolyte contact, and the formation of a stable solidelectrolyte interphase (SEI) on the Li anode by SNCE-2 enables Li|SNCE-2|Li symmetric cells to cycle stably for 1000 h at 0.2 mA cm-2. The superior cycling performance of Li|SNCE-2|NCM622 and Li|SNCE-2|LFMP cells confirms the potential of SNCE-2 for high-voltage LMBs. Furthermore, the Li|SNCE-2|LFP cells demonstrates remarkable cycling durability, maintaining 86.1% of its capacity after 1000 cycles at 0.2C. Moreover, Li|SNCE-2| LFP pouch batteries also exhibit reliable safety performance. Therefore, this work provides a promising strategy for the development of SPEs for next-generation safety solid LMBs.

Silicon-based anodes are promising candidates for next-generation lithium-ion owing to their high theoretical specific capacity. However, their practical application is limited by their severe volume expansion and poor electronic conductivity during cycling, which results in rapid capacity fading. To address these challenges, a novel polymer-derived ceramic (PDC) precursor, PSZ/PAN, was designed and synthesized by integrating polysilazane (PSZ) with polyacrylonitrile (PAN). The synthesis involved an initial free-radical polymerization of PSZ to form a crosslinked network, followed by in situ introduction and polymerization of acrylonitrile, yielding a PSZ/PAN hybrid with an interpenetrating network structure at the molecular level. Upon pyrolysis, the resulting SiCNO/C hybrid anode exhibited a high reversible specific capacity of 1050.1 mAh·g−1 at 500 mA·g−1 and excellent cycling stability, retaining 73.2

Achieving high-capacity, long-cycle-life cathodes remains one of the foremost challenges for aqueous zinc-ion batteries (AZIBs). Although vanadium-based oxides are attractive candidates, they typically suffer from sluggish Zn2+ kinetics and severe structural degradation during cycling. Herein, we report a novel graphdiyne (GDY)-encapsulated V2O5 nanofiber composite (GDY@V2O5) constructed via a directed in-situ polymerization strategy. When used as a cathode in AZIBs, the optimal GDY@V2O5 delivers an exceptional specific capacity of 571.4 mAh g(-1) at 0.05 A g(-1) and retains similar to 81% of its initial capacity after 2000 cycles at 2 A g(-1). Comprehensive structural and electrochemical analyses reveal that the GDY sheath simultaneously functions as (i) a highly conductive network that dramatically reduces charge-transfer resistance, (ii) a nanoscale pore regulator that accelerates Zn2+ diffusion ( D-Zn2 approximate to 10(-8) cm(2) s(-1)), and (iii) a robust mechanical buffer that effectively suppresses V2O5 dissolution and structural collapse. This work offers a versatile, generalizable strategy for designing high-performance electrodes for advanced energy storage systems.

Dual-modal 19F/1H MRI probes often suffer from hydrophobic aggregation caused by high fluorine content, limiting their solubility and imaging performance. Herein, a water-soluble dual-modal probe (PFCP-Gd) was developed by grafting fluorinated phosphocholine zwitterions and Gd3+ chelates onto a UV-responsive polymer via RAFT polymerization and ring-opening reactions. The design enables UV-triggered paramagnetic relaxation enhancement (PRE) modulation, allowing for activatable 19F/1H MRI contrast. Upon UV irradiation, PFCP-Gd exhibited a significantly enhanced 19F signal with a T2 relaxation time of 23 ms and a signal-to-noise ratio of 11.34 at 12 mM 19F. The probe also showed good biocompatibility and an efficient cellular uptake. This work provides a strategy for constructing water-soluble, activatable fluorinated MRI probes for dual-mode imaging.

4,4 '-Diaminodiphenylmethane (MOCA)-based cast polyurethane (CPU) elastomers possess excellent mechanical properties but often exhibit insufficient wear resistance under high-load or abrasive conditions. To address this, surface-modified silica nanoparticles (D-SiO2) were prepared using (N, N-dimethyl-3-aminopropyl)trimethoxysilane (DAPS) and incorporated into the CPU matrix via a solvent-assisted casting method. The introduced tertiary amine and organic groups on D-SiO2 facilitated covalent bonding and hydrogen bonding with the CPU, significantly enhancing interfacial compatibility and dispersion uniformity. At an optimal loading of 0.3 wt%, the composite achieved a remarkable tensile strength of 59.1 MPa and an elongation at break of 394.75%, representing a substantial improvement over the neat CPU (44.2 MPa, 376.33%). Furthermore, the wear resistance was notably enhanced, with the abrasion volume reduced by 34% compared to the unfilled system, while the friction coefficient remained stable. This work demonstrates that low-loading, surface-modified silica can effectively reinforce MOCA-based CPUs, offering a viable strategy for developing high-performance MOCA-based CPU elastomers.

The pursuit of high-performance and safe lithium batteries necessitates innovative electrolyte additives. Herein, we report a facile one-step synthesis of di(trimethylsilyl) vinylphosphonate (DTMSVP) as a multifunctional electrolyte additive. DTMSVP operates through triple synergistic mechanisms: (1) Its favorable highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels promote preferential decomposition and film formation on electrode surfaces, forming a thin and robust cathode electrolyte interphase (CEI)/solid electrolyte interphase (SEI) layer that stabilizes the interface and suppresses lithium dendrite growth; (2) The reactive siloxy groups (Si-O) group effectively scavenges HF and stabilizes PF5, mitigating transitionmetal dissolution and cathode degradation; (3) The P-Si synergistic structure imparts excellent flame retardancy, achieving a self-extinguishing time of only 1 s. With only 1 wt% addition, both the lithium iron phosphate (LFP)& Vert;Li and LiNi0.6Co0.2Mn0.2O2 (NCM622)& Vert;Li cells show significantly improved capacity retention. This work provides a simple yet effective strategy to simultaneously enhance interfacial stability, safety, and cycling performance in lithium batteries.

To address the critical issue of volume expansion in silicon-based anode materials and enhance battery performance, a novel method for synthesizing microsized silicon carbonitride (SiCNO) ceramic particles was presented as a high-performance anode material for lithium-ion batteries. SiCNO ceramic microspheres were prepared via high-temperature pyrolysis of organopolysilazane microspheres (OPSZ MPs), which were synthesized via free radical polymerization of silazane oligomers initiated by azobisisobutyronitrile (AIBN). The SiCNO microspheres, serve as the active materials in lithium-ion batteries anode, demonstrated excellent electrochemical performance with an initial discharge-specific capacity of 1663.3 mAh·g−1 and 622.9 mAh·g−1 after 400 cycles at 1 A·g−1. These microspheres exhibited superior structural stability during the lithiation and delithiation processes, with a volume expansion of 25.46

The development of all-solid-state lithium metal batteries (LMBs) demands solid polymer electrolytes (SPEs) that harmonize high ionic conductivity, electrochemical stability, and environmental sustainability. Herein, we present a molecularly engineered polycarbonate-based solid electrolyte (PCE) network synthesized via in situ ring-opening polymerization (ROP), featuring a unique cross-linked network structure of alternating carbonate-ether chemical bonds. This "rigid-flexible" architecture effectively utilizes the characteristic hierarchical structures of polymers, establishing continuous Li+ conduction pathways while suppressing crystallization. The carbonate groups enhance Li+ dissociation through weak coordination interactions, whereas the ether pendants facilitate rapid ion transport, endowing PCEs with an exceptional room-temperature ionic conductivity of 1.37 x 10-4 S cm-1 (30 degrees C) and an ultrawide electrochemical stability window up to 5.9 V vs Li+/Li. Furthermore, the cross-linked framework ensures mechanical robustness and dendrite suppression, enabling stable Li plating/stripping for over 5500 h. The assembled LFP/PCE-3/Li cell delivers remarkable cycling stability, maintaining a capacity retention rate of 85.8% after 1200 cycles. The cycling performance of LCO/PCE-3/Li and NCM622/PCE-3/Li cells demonstrates the potential applicability of PCE for sustainable, high-energy-density energy storage systems. Notably, the PCEs exhibit full degradation into nontoxic small molecules within 35 days under ambient conditions via hydrolysis of the carbonate backbone, addressing critical environmental challenges.

Graphdiyne (GDY), as an emerging carbon material, is a novel two-dimensional allotrope of carbon that possesses superior structural and performance characteristics. It not only exhibits both sp-sp2 hybridized orbitals with a high degree of π-conjugation but also features a uniformly distributed porous structure guaranteeing GDY excellent electron transfer and ion diffusion properties. Most importantly, GDY exhibits a high density of acetylene bonds, which bestow it with the ability to adsorb metallic atoms, load metal particles, and diminish the surface energy of metal particles. The strong interaction between GDY’s unique 2D scaffold and the high activity of the loaded metal species generates significant synergistic, confinement, and quantum size effects. These outstanding composite effects draw forth superior performance in various fields, including catalysis, energy storage and conversion, and biochemical. In this review, we provide a systematic overview of GDY-based composites by categorizing the metal loadings into three scales: single atoms, nanoclusters, and nanoparticles. For each category, the discussion will cover their distinct structural features, synthesis methods, material properties, and fields of application. TOC: This review provides a thorough overview of GDY-based composite, highlighting its categories, synthetic principle, applications, advantages, challenges, and opportunities.

Porous crystal films offer great potential for tackling energy and environmental challenges. However, despite over a decade of intensive research, covalent organic framework (COF) films exhibiting polyhedral textures reflective of their crystalline nature remain exceedingly rare. Here we present a scalable and adaptable biphasic strategy to synthesize pyrene (Py)-COF polyhedral crystal films with exceptional crystalline order under ambient conditions. This method enables precise control over polycrystal formation in solution and crystal growth on substrates, yielding Py-COF polyhedral films with tunable nanometer-scale thicknesses on a 4 in. wafer scale. Among them, a Py-1P film achieves a record-high Brunauer-Emmett-Teller surface area reported for COF films with comparable pore sizes alongside remarkable chemical stability. Real-space electron microscopy reveals previously unreported details of the growth of COF crystal films. These polyhedral crystal films show anisotropic thermal responses along the [001] lattice direction, with dynamically adaptive thermal expansion coefficients of (1.64-2.15) × 10-4 K-1. Through sensor testing, we correlate film crystallinity with device performance and longevity. This research expands the boundaries of COF films, revealing tremendous possibilities to advance film science and its applications.

Zwitterionic polymers are electrically neutral materials characterized by the covalent bonding of both anionic and cationic structures. They emerge as intriguing materials in rechargeable batteries and supercapacitors due to their ability to separate electrolyte ion pairs in water or organic solvents, facilitating the migration of metal ions under external electric fields. In particular, zwitterionic polymers are utilized as electrolytes to enhance metal ion conduction or as additives to improve the interfacial compatibility between electrodes and electrolytes, ultimately enhancing the overall electrochemical performance. This paper provides an overview of the structure and preparation of zwitterionic polymers specifically for energy storage devices. It also thoroughly examines their structure-performance relationships in lithium- and zinc-based batteries, as well as supercapacitors. Finally, the challenges and potential applications of zwitterionic polymers in energy storage are explored.

Bio-based dimethyl itaconate stabilizes anode and cathode interfaces via forming robust SEI/CEI; providing a sustainable, cost-effective, and industrially scalable electrolyte additive alternative to vinylene carbonate for advanced Li-ion batteries.

Multimodal imaging probes play a crucial role in overcoming the limitations associated with single-mode imaging for clinical medical diagnosis. This study focuses on the development of a photoresponsive fluorine-containing water-soluble polymer (PF) through RAFT polymerization. Subsequently, a polymer-gadolinium(III) hybrid (PF-Gd) dual-modal probe capable of T-1-weighted H-1 MRI and F-19 MRI was synthesized via postmodification of PF with a Gd-DOTA derivative. Under physiological conditions (pH = 7.4), the hybrids exhibit UV-activated F-19 NMR/MRI and enhanced H-1 MRI. The inclusion of Gd3+ facilitates the acceleration of water molecule T-1 relaxation, leading to high-intensity H-1 MRI contrast. Leveraging the paramagnetic relaxation enhancement (PRE) effect between fluorine atoms and Gd3+, the restoration of Gd3+-accelerated F-19 T-2 relaxation enables precise photoactivation of F-19 MRI signals, transitioning from the "OFF" to the "ON" state. This study provides an important reference for the development of hybrid systems that function as real-time diagnostic tools and offers controlled activation for multimodal imaging probes.

The Sto''ber method, a widely utilized sol-gel technique, stands as a green and reliable approach for preparing nanostructures on a large scale. In this study, we employed an enhanced Sto''ber method to synthesize organopolysilazane nanoparticles (OPSZ NPs), utilizing polysilazane oligomers as the primary precursor material and ammonia as the catalytic agent. By implementing a two-step addition process, control over crucial parameters facilitated the regulation of the nanoparticle size. Generally, maintaining relatively low concentrations of organopolysilazane and catalyst while adjusting the water/acetonitrile ratio can effectively enhance the surface energy of the organopolysilazane, resulting in the uniform formation of small spherical particles. The average particle size of the synthesized OPSZ NPs is about 140 nm, which were monodispersed and characterized by scanning electron microscopy, transmission electron microscopy, and dynamic light scattering. Furthermore, the composition of OPSZ NPs after pyrolysis was confirmed as SiC2.054N0.206O1.631 with 5.44 wt % free carbon structure by X-ray diffraction and energy-dispersive X-ray spectroscopy. Notably, the electrochemical performance assessment of SiCNO NPs as potential electrode materials for lithium-ion batteries exhibited promising outcomes. Specifically, at 1 A g-1 current density, the specific capacity is 585.45 mA h g-1 after 400 cycles, and the minimum capacity attenuation per cycle is only 0.1076 mA h g-1 (0.0172% of the original capacity), which indicates excellent energy storage capacity and cycle stability. In summary, this research contributes to the development of advanced anode materials for next-generation energy storage systems, marking a stride toward sustainable energy solutions.

F-19 magnetic resonance imaging (MRI)-assisted drug deliveryprovides the possibility to monitor and track drug transportationdetails in situ. A series of photo-responsive amphiphilic block copolymersconsisting of hydrophilic poly-(ethylene glycol) and F-19-containinghydrophobic segments, poly-(2,2,2-trifluoroethyl acrylate) (PTFEA),with different chain lengths were synthesized by reversible addition-fragmentationchain-transfer polymerization. In particular, the photo-sensitivefunctional group of o-nitrobenzyl oxygen was introducedto control the photolysis behavior of the copolymers under ultravioletirradiation. With the extension of the hydrophobic chain length, thedrug loading capacity and photoresponsivity were both enhanced, whilethe chain mobility of PTFEA was suppressed, and the (FMRI)-F-19 signal was attenuated. When the polymerization degree of PTFEAwas about 10, the nanoparticles exhibit detectable (FMRI)-F-19 signals and sufficient drug loading capacity (loading efficiency= 10%, cumulative release = 49%). These results offer a promising"smart" theranostic platform for F-19 MRI.

Magnetic resonance imaging (MRI) is recognized as the most powerful clinical imaging modality due to its ability to produce detailed three-dimensional anatomical images and high spatial resolution in a non-invasive manner without the use of harmful radioactive nuclides or ionizing radiation. Conventional small molecule contrast agents (CAs) for MRI, such as paramagnetic transition metal ion chelates or iron oxide nanoparticles, are limited by lower relaxivity, shorter blood circulation time and their potential toxic effects. Functional polymers capable of being detected by MRI have therefore become attractive, offering the unique advantage of pre-design due to their chemical flexibility, structural diversity, and tailoring of properties. Reversible addition-fragmentation chain-transfer (RAFT) polymerization is a powerful tool that not only enables the precise formation of macromolecular building blocks with complex structures and functions, but also provides a direct method for preparation of polymeric nanoparticles with multiple morphologies suitable for biomedical applications. In addition, when combining RAFT polymers with inorganic/metallic complex nanocomposites, the polymer provides the ability to encapsulate therapeutic molecules, thereby combining diagnostic and therapeutic functions in what is known as a theranostic nanomedicine. In this review, we highlight recent advances in the development of multifunctional polymers as MRI CAs designed and prepared by RAFT polymerization and their performance in diagnosis and treatment of disease. In addition, the review will address the challenges and future opportunities for RAFT-mediated MRI-based theranostics in guiding the treatment of diseases including malignant tumors.

Fluorine-19 magnetic resonance imaging (19F MRI) probes have received considerable research interest as imaging contrast agents (CAs), but they remain neglected and underutilized due to the limited fluorine content or poor performance of fluorinated tracers. Here, we present polymeric nanoparticles (NPs) as 19F MRI CAs with a simple synthesis method and promising imaging performance. First, hydrophilic random copolymers were synthesized from oligo(ethylene glycol) methyl ether acrylate and perfluoropolyether methacrylate by reversible addition-fragmentation chain transfer (RAFT) polymerization. The optimal fluorine content, polymer concentration, and cytotoxicity as 19F MRI CAs were investigated in detail. Then, the optimal copolymer was selected as the macromolecular chain transfer agent, and the chain extension was performed with 2-(perfluorooctyl ethyl methacrylate). Subsequently, the NPs with different morphologies, such as ellipsoidal, spherical nanoparticles and vesicles, were prepared in situ by the RAFT-mediated polymerization-induced self-assembly method. In addition, the 19F MRI signal and cytotoxicity studies further confirmed that these polymeric NPs are nontoxic and have great potential as promising 19F MRI CAs for biological applications.

The direct catalytic asymmetric hydrogenation of pyridines for the synthesis of piperidines remains a challenge. Herein, we report a one-pot asymmetric hydrogenation of pyridines with subsequent N-alkylation using a traceless Brønsted acid activation strategy. Catalyzed by an iridium-BINAP complex, the substrates undergo ketone reduction, cyclization and pyridine hydrogenation in sequence to form indolizidines and quinolizidines. The absolute configuration of the stereocenter of the alcohol is retained and influences the formation of the second stereocenter. Experimental and theoretical mechanistic studies reveal that the chloride anion and certain noncovalent interactions govern the stereoselectivity of the cascade reaction throughout the catalytic process.

Polyethylene glycol (PEG) used as solid polymer electrolyte has shown disadvantages of low ionic conductivity and lithium ion transference number due to its high crystallinity. In this study, we propose Passerini three -component polymerization (P-3CP) to modify PEGs for solid polymer electrolytes (SPEs). Thus, a series of PEG-based polyesters (PGPEs) with molar masses between 14,400 and 30,200 gmol-1 are synthesized by P-3CP. The crystallinity of obtained PGPEs is successfully suppressed by the introduction of side groups via P-3CP. SPEs consisting of PGPEs as matrix and bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) with different con-centrations were investigated in detail. The SPE composed of PGPE-4000 with 30 wt% LiTFSI presented the best ionic conductivities of 5.85 x 10-5 Scm(-1) and 1.94 x 10-3 Scm(-1) at room temperature and 80 C, respectively, which are significantly higher than the commonly used PEG-based SPE. The LiFePO4/Li solid-state lithium-ion battery assembled with PGPE-based SPE showed excellent cycle stability. After 100 cycles at 0.5C at 60 C, the discharge specific capacity remains 133 mAhg(-1). Furthermore, due to the addition of amide side groups, the flame retardant property of PGPE-based SPEs is improved. Compared to PEG, the limiting oxygen index (LOI) values increase from 21.0 to 25.5 after modification by P-3CP. Therefore, the P-3CP is an attractive method to obtain polyesters from dicarboxylic acid or diol monomers for the application in the lithium battery field.

Hyperbranched aliphatic polycarbonates (HBPCs) have attracted significant attention in the field of biomedical application owing to their abundant end groups, biocompatibility, and nontoxic degradation products. However, their practical application is hampered by tedious synthesis procedures. The present work described a novel organo-catalyzed "A1+B2"-ring-opening polymerization (ROP) using a monofunctional primary alcohol (A1) as an initiator and a bicyclic carbonate monomer (B2) for the straightforward synthesis of HBPCs under mild conditions. No gelation was observed up to 90% conversion of the cyclic carbonate ring. HBPCs with molar masses in the range from 7 to 20 kg/mol were obtained. Based on the "A1+B2"-ROP, HBPCs bearing a variety of functionalities including alkene, alkyne, aldehyde, furan, azide, and mPEG groups, which are of great significance in the field of click chemistry, have been successfully prepared by using functional alcoholic initiators. This polymerization strategy allowed for precise control over the HBPC structure: (1) the hyperbranched polymer (HBP) backbone can be adjusted by design of a bicyclic carbonate monomer with various linkages; (2) the use of an appropriate initiator leads to the introduction of functional end groups. Overall, the "A1+B2"-ROP provides an efficient method for preparing a variety of HBPs like hyperbranched polyester, polyether, polyphosphate, and poly(amino acid) with complex architectures in a single step.