Aug 2026· Angewandte Chemie· pp.
e2761225
· 0 citations· 25 references
Medicine
Abstract
Ultra-small nanoparticles (USNPs), characterized by fast dynamics, ultra-small dimensions and dense surface functionalities, offer an underexplored yet powerful strategy to simultaneously modulate polymer behavior and NP assembly. Herein, we introduce a versatile materials design strategy based on USNP complexation to reprogram polymer chain dynamics and manipulate NP ordering. Using 1 nm metal oxide NP, H3PW12O40 (PTA) complexed with polyvinyl alcohol (PVA), we show that USNPs induce anomalous viscosity reduction via chain collapse, enabling residual-stress-free film fabrication. The size of PTA, significantly smaller than the polymer coil dimensions, combined with strong attractive interactions to PVA chains, induces chain collapse in solution. Their ultrahigh surface area disrupts polymer crystallinity and forms humidity-responsive supramolecular networks, demonstrating a humidity‑assisted proof‑of‑concept route for optical‑film orientation and fixation. Moreover, the energy barrier for USNP dynamics is substantially lower than that of colloidal NPs, allowing stretch-induced orientation under uniaxial extension. In situ x-ray scattering confirms unidirectional PTA orientation upon mechanical stretching, yielding promising birefringence (Δn ≈ 0.018). This work establishes USNP complexation as a versatile strategy to simultaneously reprogram polymer processability and achieve precise NP ordering for functional devices.
The polymer dynamics at the nanoscale exhibit significant deviations from their bulk materials, affecting both our fundamental understanding and practical applications of polymers. Despite growing applications and synthesis advancements of 3-dimensional confined polymeric nanomaterials, comprehensive studies of their dynamics remain scarce, mainly due to a lack of suitable characterization techniques. In this study, we employed temperature-controllable dark-field microscopy to visualize the thermally activated segmental and whole-chain motions of individual polystyrene nanoparticles (PSNPs), achieved by quantitatively tracking deformation-induced changes in their optical scattering intensity during heating. Single-particle measurement enables the determination of intrinsic deformation temperatures by eliminating average effects, inevitable interparticle interactions, and the potential influence of thermal equilibrium that commonly exists in conventional bulk measurements. Building on this foundation, a longer confinement length scale for whole-chain motion compared to segmental motion was observed in single PSNPs. This distinct size dependency further suggested that the particle size, in addition to molecular weight, also played a great role in influencing the entanglements within PSNPs. The synergistic effects of these two structural factors on chain entanglement were further mapped, revealing that the rubber plateau of single PSNPs began to narrow when the particle size decreased to approximately 20 times the radius of gyration of the constituent polymer chains. This study presents a platform for imaging the thermally activated chain mobility of 3D-confined polymeric nanoparticles, expanding single-particle scale insights into how nanoscale confinement affects polymer entanglements and providing guidance for their further applications.
Xinyu Wang, Long Zhao, Wei Wang et al.· ACS Nano· 0 citations
Eutectogels hold considerable promise for applications in flexible electronics, soft robotics, and protective systems owing to their combination of the environmental stability of deep eutectic solvents and the mechanical robustness of polymer networks. However, predominantly weak intermolecular interactions among polymer chains within eutectogels restrict their mechanical performance, making it challenging to simultaneously achieve high strength and high toughness. Herein, we propose an inorganic ionic polymerization‐anchored polymer network (IIP‐APN) strategy to construct ultrastrong and ultratough eutectogels. Specifically, calcium phosphate oligomers (CPO) are incorporated into the polyvinyl alcohol (PVA) chain network to serve as nanoanchors. Through inorganic ionic polymerization, hydroxyapatite nanorivets are generated to anchor PVA chains, forming a hierarchically integrated organic–inorganic composite network. This unique riveting network structure imparts record‐breaking ultrahigh toughness (696.4 ± 119.1 MJ m−3) and high strength (58.02 ± 3.87 MPa) to the resulting PVA/CPO eutectogels, significantly surpassing existing gel materials. Moreover, the PVA/CPO eutectogels demonstrate excellent energy absorption and dissipation, outstanding fatigue resistance over 8000 cycles, and the capacity for damage repair via secondary inorganic ionic polymerization. Consequently, PVA/CPO eutectogels exhibit significant potential for technological applications. The proposed IIP‐APN strategy provides a powerful platform for the design and development of high‐performance gel materials.
Bowen Zhang, Yongjin Du, Xiaotong Sun et al.· Advances in Materials· 0 citations
Colloidal molecules (CMs) are assemblies of nanoparticles (NPs) that accurately replicate the structure and symmetry of actual molecules. Regarded as modular building blocks, CMs enable the creation of hierarchical structures that are challenging to achieve through the direct self-assembly of individual NPs. However, the limited availability of efficient and scalable methods for nanoscale CM synthesis has constrained their broader use in constructing hierarchical structures. Here we show that long-range electrostatic attraction, combined with short-range hydrogen-bonding interactions, enables the assembly of binary NPs into CMs in an aqueous medium, attaining high yields of up to 95% and concentrations three orders of magnitude higher than previously reported values. These CMs can serve as building blocks for constructing CM arrays and non-close-packed hierarchical structures with open pores. Our approach marks an efficient self-assembly strategy for fabricating nanoscale CMs and demonstrates their potential in constructing innovative hierarchical structures. Colloidal molecules mimic real molecules and can serve as nanoscale building blocks. Here, the authors use dialysis-guided aqueous self-assembly to produce them with high yield and concentration, highlighting their potential for hierarchical structure formation.
Nanoparticle (NP) assemblies exhibit collective optical, electronic, and magnetic properties that enable applications in sensing, catalysis, energy conversion, and optoelectronics. However, achieving independent control over structural integrity and surface functionality within such assemblies remains a significant challenge in NP self-assembly. Here, we report a modular post-functionalization strategy that decouples structural locking from surface reprogramming in colloidal molecules (CMs). ABn symmetry CMs assembled from complementary polymer-grafted Au NPs were selected as representative models and reinforced using multivalent N-heterocyclic carbene (NHC)-containing block copolymers. The NHC anchoring segments form robust C–Au bonds, converting initially noncovalent interparticle junctions into covalently bridged connections without perturbing predefined geometries. This multivalent locking reduces interparticle spacing, enhances plasmonic coupling, and significantly improves chemical, ionic, thermal, and mechanical stability, preserving three-dimensional architectures in the dry state. Importantly, separation of anchoring and functional polymer blocks enables independent introduction of amphiphilic and light-responsive surface properties, allowing solvent-dependent plasmonic modulation and reversible light-triggered hierarchical assembly while maintaining discrete CM geometry.
Runshi Qiao, Huaining Zha, Jing Tao et al.· Nano Reseach· 0 citations
Ultrathin transparent photonic films that are simultaneously robust, cytocompatible, and actively antimicrobial remain rare. Here, the critical physical properties of freestanding micrometer-thick films composed of layered cellulose nanofibers intercalated with Ti3C2Tx MXene nanosheets (CNF-MXene) are established. Correlated co-alignment of MXene flakes with near-perfect in-plane order is achieved in the cellulose nanofiber matrix by vacuum-assisted filtration. The Herman's orientation parameter of MXene nanosheets reaches up to 0.94, approaching the theoretical limit of 1.0 for perfect orientational order. Flow-assisted alignment and nanofiber-mediated confinement are proposed to suppress MXene restacking and lock the unique film architecture into a stable scaffold. This highly ordered structure yields a significant increase in mechanical strength and elastic modulus. Moreover, co-alignment of individual flakes at ultralow volume fractions (below 1%) creates accessible, photothermally active surface sites within optically clear films. As a result, these ultrathin CNF-MXene membranes combine near-infrared-activated photothermal antimicrobial behavior and molecular adsorption of organic dye as a proxy for accessibility, highlighting a distinctive multifunctional platform for active bio-based films with strong potential for wound-healing applications and long-term functionality preservation.
Valeriia Poliukhova, Jacob Crossno, K. Diedkova et al.· Small· 0 citations
Monodisperse porous polymer spheres are functional materials with attractive properties such as high cohesive strength, strong adsorptivity, and a high degree of surface functionalization due to their large specific surface area. They are widely used in various fields, including biomedicine, instrumental analytics as stationary phases in HPLC columns, and sensor technology. In this work, the formation mechanism of porous poly(glycidyl methacrylate-co-ethylene dimethacrylate) (p(GMA-co-EDMA)) particles was investigated in a time-resolved experiment using scanning electron microscopy (SEM) and two-dimensional confocal Raman spectroscopy. Data analysis revealed that the particles are formed via rapidly reacting anisotropic Janus-like intermediates that assemble into large agglomerates of different morphologies. Spectral unmixing of the Raman data enabled the determination of relative concentration changes in the reactants over time. This study uncovers a pool of previously unknown anisotropic particle species that offer new opportunities for subsequent functionalization and material design.
Alexandra Wagner, Julia Schwabe, F. Wackenhut et al.· Polymers· 0 citations
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