Porous materials including hydrogels offer high potential for applications requiring controlled mass transport, cell infiltration, and mechanical properties, such as tissue engineering, drug delivery, or soft robotics. We report a facile method for the synthesis of hydrogels and microgels with tunable porosity, offering control over diffusivity and mechanical properties. By exploiting the cononsolvency of polymers based on dimethylacrylamide (DMAAm) and hydroxyethylacrylamide (HEAAm) in water-acetonitrile mixtures, we produce porous networks with adjustable pore sizes up to several micrometers by varying the acetonitrile content in aqueous solution used during synthesis. The adjustment of the pore size by variation of the solvent mixture allows for fine-tuning of the hydrogel and microgel mechanical and diffusion properties with stiffnesses ranging from a few kPa up to more than 100 kPa and diffusion coefficients of 4 kDa FITC-dextran varying from 50 to over 130 µm2 s-1. Detailed analyses using optical microscopy, (cryo-)scanning electron microscopy, rheology, nanoindentation, and fluorescence recovery after photobleaching confirm the dependence of the observed properties on the network morphology and the similarity of the pore size and interconnectivity between hydrogel and microgel samples. The obtained hydrogels and microgels show strong potential for applications in bioengineering, sensing, and responsive materials.
Poly (vinyl alcohol) (PVA), a representative biodegradable and water-soluble polymer, suffers from high crystallinity, a strength‑toughness trade‑off, and poor thermal stability arising from strong interchain hydrogen bonding. Conventional modification strategies fail to simultaneously achieve synergistic enhancement of strength-toughness and functionalization, severely restricting its engineering applications. Herein, inspired by the robust yet dynamic nature of cation-π interactions, we present a universal design strategy for high-performance water-soluble polymers based on indole-Mg2+ cation-π dynamic cross-linking. Molecular simulations and spectroscopic characterization demonstrate that Mg2+ forms strong cation-π interactions with indole moieties, exhibiting a binding energy of -113 kJ mol-1. Mechanical testing reveals that the optimally formulated PVAI-7.5%Mg2+ film achieves a tensile strength of 51 MPa (a 130% increase from 22 MPa) and an elongation at break of 400% (enhanced from 320%), thereby realizing synchronous improvement of strength and toughness. Benefiting from the dynamic reversibility of cation-π interactions, the film exhibits autonomous scratch healing within 12 h at room temperature without external stimuli, while retaining excellent water solubility that enables multiple recovery and reprocessing cycles via solvent-based methods without performance degradation. This study overcomes the dual bottlenecks of the strength-toughness trade-off and the performance-functionalization incompatibility inherent to PVA modification, offering new avenues for the high-performance and multifunctional design of water-soluble polymers and providing experimental and theoretical insights into the application of cation-π interactions in polymeric materials.
Limitations of conventional small molecule protonic acids used for doping polyaniline (PANI) including rapid performance degradation, potential cytotoxic effects, and the risk of provoking tissue inflammation; these pose significant challenges for biomedical applications. To overcome these issues, the use of poly(4-styrenesulfonic acid) (PSS) as a macromolecular dopant is proposed in this work; a stable PANI: PSS is synthesized and employed as an electrode material. This electrode material is integrated with a gel electrolyte formulated from gelatin and carboxylated chitosan to construct an all-in-one supercapacitor. This integrated design effectively eliminates interfacial resistance between the electrode and the electrolyte while simultaneously enhancing the mechanical integrity and operational stability of the device under physiological conditions. The all-in-one supercapacitor constructed by PANI: PSS as the electrode material demonstrates notable electrochemical performance, characterized by high specific capacitance, excellent long-term cycling stability, and reliable rate capability. Furthermore, comprehensive in vitro biocompatibility evaluations of the all-in-one supercapacitor are conducted, which reveal minimal cytotoxicity, no significant induction of inflammatory responses, and high blood compatibility, especially anticoagulant properties. These findings confirm the material suitability for use in implantable biomedical devices, and this study establishes a practical and reliable strategy for the development of safe, efficient, and biocompatible power sources.
Dielectric polymers with high glass transition temperatures (Tg) are widely employed in capacitive energy storage applications for electronic equipment and power systems. However, polyetherimide (PEI) suffers from significant leakage current and a pronounced increase in conductivity loss at high temperatures, which prominently restricts its operational reliability under extreme conditions. In this work, an all-organic strategy is proposed by random blocking the 2, 2-Bis [4-(4-aminophenoxy) phenyl] propane (BAPP) into the PEI backbones. The staggered potential barriers between distinct chains create local electronic trap states and increase the energy barrier for trapped carriers to escape. Furthermore, the incorporation of the BAPP segments effectively decreases the interchain spacing and fractional free volume (FFV). Experimental studies and density functional theory (DFT) calculations reveal that a large number of deep traps combined with a reduced FFV, enhance electron capture capability and restrict charge transport. As a result, the random copolymer with 50 mol% BAPP segments (C50PEI) exhibits superior high-temperature capacitive performance, delivering an exceptional discharged energy density (Ue) of 4.68 J/cm3 with a charge-discharge efficiency (𝜂) exceeding 90% at 200°C. This work provides an all-organic design strategy for the development of dielectric capacitors under extreme high-temperature conditions.
Machine learning is now a productive tool in polymer research, predicting many properties and proposing new structures by generative design. For the materials whose behaviour is set by processing rather than chemistry alone, our capacity to propose polymers is beginning to outrun our capacity to make, process, and validate them. This Perspective argues that a key bottleneck for these materials is not model architecture but a polymer-specific gap: macroscopic, processing-dependent properties and slow validation timescales. I distinguish chemistry-dominated, condition-dependent, and process-history-dependent properties, and develop two contrasting cases: sustainable thermoplastics, governed by melt flow and thermal history, and supramolecular hydrogels, governed by aqueous self-assembly. I propose and stress-test a self-driving laboratory built around the parts the autonomous-materials literature has under-served for polymers: handling viscous, non-Newtonian melts and sol-gel transitions; preserving shear and thermal history; surrogate simulators to keep the loop fast; and mechanism-preserving accelerated tests for slow properties. The contribution is not the closed loop, which is well established, but the claim that, for non-dilute melts, concentrated solutions, and assembled soft matter, and for properties whose validation runs to months or years, polymer process physics and slow-property validation are among its principal frontiers. Investing there turns computational acceleration into deployed materials.
Fiber-reinforced elastomers can significantly enhance mechanical strength while retaining material softness, thereby expanding the application scope of elastomeric materials in scenarios requiring both high flexibility and high strength. Compared with thermoplastic polymers and ceramic materials, elastomers exhibit low modulus and high fracture strain, which result in more complex fiber-matrix interfacial behaviors. This review systematically elucidates the intrinsic relationships between microscopic stress transfer mechanisms and macroscopic mechanical properties in fiber-reinforced elastomers, summarizes research progress in this field over the past two decades, and highlights the effects of various reinforcement strategies on performance optimization, providing a theoretical basis for the design and development of next-generation high-performance fiber-reinforced elastomers.
A simple one-step photopolymerization strategy is presented to fabricate multifunctional shape-memory polymer composites capable of remote and programmable light-triggered actuation. The composites integrate gold nanoparticles and semicrystalline poly(ethylene)-block-poly(ethylene oxide) nanoribbons within a cross-linked epoxy network. During curing, the block copolymer undergoes crystallization-driven self-assembly, generating micrometer-long nanoribbons that act as reversible thermal switching domains, while gold nanoparticles are simultaneously formed in situ, enabling efficient conversion of visible light into localized heat through plasmonic excitation. Spectroscopic and microscopic analyses confirm the successful incorporation of both components without compromising their native morphology. Differential scanning calorimetry reveals two distinct thermal events corresponding to the glass transition of the epoxy matrix and the melting of the polyethylene domains, providing two independently addressable switching temperatures. Under green-light irradiation, the embedded gold nanoparticles rapidly raise the local temperature, enabling not only remote activation of the shape-memory effect but also programmable sequential shape recovery by selectively activating each thermal transition through laser power adjustment. These results demonstrate that combining crystalline block copolymer nanostructures with plasmonic nanoparticles enables remotely controlled multi-stage actuation using a single external stimulus. This scalable and ambient-compatible approach provides a versatile platform for the design of light-responsive composites with tunable thermal and mechanical behavior, offering opportunities for applications in smart coatings, remote actuators, and programmable materials.
UV absorbers are essential for long-term durability, yet boosting UV absorption without visible coloration presents a classic trade-off. We present an automated, high-throughput design platform that balances these objectives by optimizing site-substituent patterns on a benzophenone (BP) scaffold. Solar-weighted kinetic metrics quantify the UV-band rate constant (kUV) and the visible-band rate constant (kvis). Guided by favorable site-substituent rules, a focused design yields candidates with high kUV and near-zero kvis. The lead candidate is identified as a high-potential candidate, with a predicted kUV = 5.28 × 10-3 s-1 (≈ 260 × that of commercial BP, 2.06 × 10-5 s-1) with an estimated negligible visible absorption. Compared with BP, the leader one exhibits a broad, strong absorption band in the 275-350 nm range, yielding extended and enhanced UV absorption. These results overturn the perceived trade-off between high UV absorption and colorlessness. The platform provides rapid, computationally-informed design directions that shortens development cycles and reduces costs, replacing ad hoc few-molecule computations with a generalizable, reusable framework across polymer systems.
The persistent toxicity of phenolic contaminants necessitates the development of integrated water remediation technologies. While the synergistic "trap-and-destroy" pathway-combining rapid adsorption with in-situ photocatalytic degradation-is highly promising, its practical deployment is often hindered by the aggregation-caused quenching (ACQ) of organic chromophores and the recovery challenges associated with suspended powder catalysts. This work proposes a topology-directed engineering strategy to fabricate a macroscopic, metal-free material (PCSOA) by crosslinking perylene diimides with rigid polyhedral oligomeric silsesquioxane (POSS or SQs) cages. DFT calculations suggest that the rigid POSS nodes provide strong structural constraint to restrict the molecular motion of the photoactive perylene units, thereby suppressing non-radiative decay pathways while largely preserving the intrinsic frontier molecular orbitals. Driven by strong electrostatic and π-π affinities, the highly polarized network captures trinitrophenol with an uptake reaching 929 mg g-1. By gathering target molecules directly around the active sites, this localized accumulation significantly enhances visible-light photoactivity. Consequently, the system delivers a phenol mineralization rate constant of 1.79 h- 1 and removes over 98% of the total organic carbon (TOC). From a practical standpoint, formatting the material into a macroscopic aerogel bypasses the cumbersome separation steps inherent to powders, allowing for stable and high-throughput water treatment in continuous-flow setups.
Schiff base derivatives, namely 3-(((2-hydroxynaphthalen-1-yl)methylene)amino)-1-phenyl-1-pyrazole-5-one (3-APPHNA) and 4-(((2-hydroxynaphthalen-1-yl)methylene)amino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3-one (4-APPHNA), were synthesized via the condensation reaction of 3-amino-1-phenyl-2-pyrazolin-5-one (3-APP) and 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, (4-APP) with 2-hydroxynaphthaldehyde (2-HNA) in ethanol. Synthesized monomers were then converted into their oligomeric derivatives via oxidative polycondensation carried out using NaOCl. The structural, thermal, optical, electrochemical, and morphological properties of the obtained monomers were comprehensively characterized using fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H-NMR), carbon-13 nuclear magnetic resonance (1 3C-NMR), ultraviolet-visible spectrophotometer (UV-vis), thermogravimetry-derivative thermogravimetry (TG-DTG), and cyclic voltammetric analyses. Spectroscopic studies confirmed the successful synthesis of Schiff bases and the presence of stable azomethine bonds. Molecular weight, glass transition temperature, and surface morphologies of oligomers were determined by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and field emission scanning electron microscope (FE-SEM) measurements, respectively. The Mn values of oligo(3-APPHNA) and oligo(4-APPHNA) were found to be 3400 and 2900 Da, respectively. The results revealed an oxidative oligomerization process yielding relatively narrow molecular weight distributions. Oligo(4-APPHNA) has shown more pronounced semiconductor properties compared to other oligomers, considering its 2.30 eV optical band gap and frequency-dependent electrical behavior. Additionally, dielectric measurements showed that oligo(4-APPHNA) exhibited higher dielectric constant, dielectric loss, and AC conductivity values throughout the investigated frequency range. These findings suggest that the synthesized oligomers are promising candidate materials for future optoelectronic and semiconductor applications, but further research at the device level is needed.
Charge-shifting polycations based on poly(2-(N,N-dimethylamino)ethyl acrylate) (PDMAEA) are promising materials for forming polyelectrolyte complexes relevant to biomedicine. Their complexation behavior can be tuned by incorporating a controlled fraction of permanently charged quaternary ammonium units. This strategy relies on the homogeneous distribution of these units while maintaining charge-shifting properties of PDMAEA. Herein, we report the reversible addition-fragmentation chain-transfer copolymerization of 2-(N,N-dimethylamino)ethyl acrylate (DMAEA) and 2-acryloxyethyltrimethylammonium chloride (AETAC). Optimized conditions afford copolymers with molecular weights of 26 000-130 000 g/mol and dispersities below 1.1, with good agreement between theoretical and experimental compositions. Reactivity ratios close to unity indicate near-statistical copolymerization and a homogeneous distribution of AETAC units along the chains. Hydrolysis studies showed that incorporating up to 40 mol% AETAC negligibly influenced the rate of DMAEA hydrolysis. In contrast, isothermal titration calorimetry revealed that increasing the AETAC content resulted in three times more heparin molecules bound per copolymer chain for copolymers between 10 and 40 mol% AETAC, while reducing the number of binding contacts per heparin molecule. The results demonstrate that the precise compositional control achieved under the proposed polymerization conditions enables tuning of the complexation behavior of DMAEA-based copolymers, which may be useful for the design of biomedical polyelectrolyte platforms.
High-performance polymeric materials with low dielectric constants are critically required for next-generation high-frequency communication. Benzoxazine resins have attracted considerable attention as promising candidates due to their flexible molecular design, excellent thermal stability, low water absorption, and inherently low dielectric properties. However, most low-dielectric materials from benzoxazine systems have been developed using conventional manufacturing techniques, while their integration into additive manufacturing remains largely unexplored. In particular, adapting benzoxazine resins for vat photopolymerization (VPP) presents significant challenges because benzoxazines typically undergo thermally initiated ring-opening polymerization rather than direct photopolymerization. This review provides an overview of recent advances in the development of photoreactive benzoxazine systems and VPP-compatible resin formulations. Particular emphasis is placed on molecular design strategies, the incorporation of photocurable functional groups, control of resin viscosity, and dual-curing mechanisms that combine photocuring with subsequent thermal ring-opening polymerization. The reported studies demonstrate promising progress toward the fabrication of benzoxazine-based structures with favorable thermomechanical performance and processing feasibility. Furthermore, this review critically discusses current formulation strategies and emerging design principles for developing low-dielectric benzoxazine resins. The insights presented here aim to guide future research toward the development of advanced benzoxazine materials suitable for additive manufacturing of high-performance components in next-generation high-frequency electronic devices.
Polyimides (PIs) are widely used as advanced substrates due to their excellent thermal and mechanical properties. However, conventional petroleum-based aromatic PIs suffer from intrinsic coloration arising from charge-transfer complex (CTC) formation, limiting their optoelectronic applications. In this study, two camphor-derived alicyclic diamines (CA and CM) were synthesized, along with a reference isosorbide-derived diamine (IS). These monomers were polymerized with 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) and a tetracarboxylic dianhydride featuring a cyclopentanone bis-spironorbornane structure (Cp) to prepare six biobased CPIs. Their favorable optical transparency arises from the combined contribution of the non-conjugated dianhydride structures and the alicyclic camphor-derived diamine structures. The structure-property relationships of the biobased CPIs were systematically investigated. The CA series exhibits limited film-forming ability because of its highly rigid molecular structure. In contrast, incorporating a methylene spacer into the CM series enhanced chain flexibility, leading to improved film-forming ability and overall film quality. Among the prepared CPIs, CM-CB exhibited the most balanced performance, achieving 60% biomass content, optical transparency (T400 = 82% and YI = 3), and a glass transition temperature above 300°C. These results suggest that camphor-derived diamines can serve as useful biobased units for developing CPIs with balanced optical transparency and thermal properties.
Covalent adaptable networks (CANs) are potentially considered as a viable alternative to one-time use plastics and their stimuli responsiveness render them suitable for application in a range of functional domains. However, most of the CANs reported in literature are based on a single dynamic linkage. In this report, we explore a biobased functional motif for synthesis of thioacetal based CANs, which may be suitably functionalized to serve as a precursor for CANs with multiple dynamic linkages such as thioacetal, thia-Michael adduct and Diels Alder adduct. This opens the window for tailoring mechanical and responsive behavior of the resulting CANs. As a proof of concept, 5-hydroxymethylfurfural is utilized for the synthesis of thioacetal based CANs (PEMP-HMF-n) in presence of a tetra-thiol crosslinker and its acrylate functionalized derivative is exploited for multi dynamic linkage-based CAN (PEMP-HMFA-n) in presence of the above crosslinker. The resulting PEMP-HMFA-n films display five-time increase in tensile stress value compared to that of the PEMP-HMF-n supporting the design philosophy.
A novel method was developed to synthesize composites of Cu-BTC with alginate. The gelation was triggered by the open Cu metal centers which are coordinated to the BTC ligands. The resulting gel was dried supercritically to obtain the aerogel composite. Cu-BTC content in the composite was tuned in to the mass ratio of 1:2 to 2:1 and the resulting materials' BET surface areas ranged between 450 and 1162 m2/g. The equilibrium uptake of CO2 for AlgA/Cu-BTC (2:1), AlgA/Cu-BTC (1:1), and AlgA/Cu-BTC (1:2) at 1 bar and 298 K was determined as 0.132, 0.325, and 0.434 mmol g-1, respectively for a binary mixture of 15% CO2/85% N2. Uptake values determined by dynamic adsorption experiments were slightly lower than those obtained for single-component CO2 conditions, which was attributed to competitive adsorption between CO2 and N2. The simulated CO2 adsorption isotherms slightly overestimated the experimental uptake values, which is consistent with the involvement of open Cu metal centers in the gelation of sodium alginate. This is the first time that a MOF is utilized as a gelation triggering agent and is likely to lead to the development of novel nanostructured alginate aerogel/gel composites of MOFs with divalent cation centers.
While immunotherapy has revolutionized cancer treatment, its clinical efficacy is still constrained by tumor heterogeneity, acquired drug resistance, and the immunosuppressive tumor microenvironment. Traditional apoptosis-driven cancer therapeutic strategies are often inefficient and immunologically silent. In contrast, non-apoptotic programmed cell death (PCD) pathways (ferroptosis, pyroptosis, necroptosis, and cuproptosis) offer high immunogenicity and the ability to bypass resistance mechanisms, yet their clinical application is limited by poor tumor specificity, off-target toxicity, and delivery inefficiency. Peptide self‑assembly technology has emerged as a powerful platform to address these challenges, enabling enzyme‑responsive morphological transformation, multivalent target binding, subcellular localization, multifunctional co‑assembly, and artificial enzyme mimicry for precise PCD induction. Despite significant progress, a systematic classification of how peptide assemblies trigger distinct PCD pathways is still lacking. This review categorizes peptide self‑assembly‑induced tumor cell death into five major themes, including ferroptosis, pyroptosis, necroptosis, cuproptosis, and combined death. By summarizing the design principles, key evidence, and anti‑tumor outcomes, this review highlights the unique advantages of peptide self‑assembly. It provides a theoretical foundation for developing peptide‑based precision cancer therapies and aims to guide future research toward clinical translation and personalized treatment.
The development of nonviral RNA delivery has been shaped by the chemistry of cationic materials and their capacity to organize nucleic acids through multivalent electrostatic interactions. Before ionizable lipid nanoparticle (LNP) formulations became central to clinically translated RNA therapeutics, nonviral nucleic acid delivery relied largely on cationic liposomes, cationic polymers, and polymer-lipid complexes that condensed anionic DNA or RNA into nanoscale assemblies. These systems established principles that continue to guide RNA nanomedicine, including electrostatic complexation, colloidal assembly, endosomal trafficking, charge-associated toxicity, degradable carrier design, and intracellular cargo release. Over the past decade, the clinical success of mRNA vaccines has consolidated small-molecule ionizable lipid LNPs as a major formulation platform, owing to their ability to combine efficient RNA encapsulation with improved tolerability, manufacturability, and in vivo expression. This Perspective revisits cationic polymer-lipid nanoparticles not as historical precursors to ionizable lipid LNPs, but as a macromolecular materials space that can clarify and extend current RNA delivery design. We discuss these systems within a structure-assembly-biointerface framework, emphasizing how polymer architecture, charge distribution, degradability, topology, and polymer-lipid interfacial organization govern RNA packaging, nanoparticle formation, intracellular release, tissue-selective interactions, and biological identity.
The molecular engineering of the A-D-A'-D-A type non-fullerene acceptors (NFAs) at the core has generated a diverse of high-performance acceptor materials. Recently, transformation of the benzothiadiazole (BT) core to benzimidazole (Im), which is a widely used unit in constructing functional framework, cluster or carbene based materials, has been explored with a series of Im-based NFAs, which displayed attractive optoelectronic properties. However, the more general synthetic route remains necessary for further exploration of this kind of NFAs. Herein, we applied the typical approach for Im structures by using o-benzoquinone and aldehyde in the presence of ammonium acetate yielding the target NFAs effectively, and three new Im-based acceptors were obtained by adjusting the hanging groups with benzene, 4-fluorobenzene and 3.5-difluorobenzene. These NFAs displayed tunable molecular dipole moments, UV-vis absorption, and frontier energy levels. When used as the guest acceptor in the PM6:BTP-eC9 based organic solar cells, the fluorinated NFAs can effectively improve the device efficiency to 19.48%, which is significantly higher than 18.42% of the binary control and also among top efficiencies for cells using Im-based NFAs. This work provides an effective protocol for Im-based NFAs with tunable molecular scaffolds and properties, which can be of great potential for optoelectronics.
α-Ethylidene-δ-vinyl-δ-valerolactone (EVL), a trifunctional monomer derived from CO2 and 1,3-butadiene, provides a versatile platform for the construction of functional polyesters. A furan-functionalized monomer (EVL-FML), synthesized via thiol-Michael addition of EVL, exhibits a low ceiling temperature (Tc = -102.4°C) that precludes its homopolymerization. To overcome this thermodynamic limitation, EVL-FML is copolymerized with the Michael adduct of EVL and 1-propanethiol (EVL-SPr), which possesses a higher Tc of -2.4°C. Catalyzed by 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), the ring-opening copolymerization (ROCP) yields polyesters bearing furan groups (PF-x, 0-50 mol%) with number-average molecular weights up to 13.1 kg mol-1, and narrow distributions (Ð < 1.2). Kinetic studies reveal that the ROCP follows pseudo-first-order kinetics, with a reaction order of 0.37 with respect to TBD. The reactivity ratios are determined to be rEVL-SPr = 0.94 and rEVL-FML = 0.75. Subsequently, maleimide-functionalized (13-59 mol%) polyesters (PM-y) are prepared via post-polymerization modification of PEVL-SPr. Thermally reversible covalent adaptable networks (CANs) are constructed through the Diels-Alder reaction between PF-x and PM-y, exhibiting cross-link densities ranging from 110 to 572 mol m-3 and tensile strengths between 0.42 and 12.45 MPa. These networks demonstrate excellent self-healing, reprocessability, and inherent degradability, offering a promising pathway toward sustainable functional materials.
