We exploited the monomer-feeding mechanism of reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization to achieve the successful polymerization-induced self-assembly (PISA) of asymmetric divinyl monomers. Colloidally stable cross-linked block copolymer nanoparticles with various morphologies, such as vesicles, were directly prepared at high solids. Morphologies of the cross-linked block copolymer nanoparticles could be controlled by varying the monomer concentration, degree of polymerization (DP) of the core-forming block, and length of the macro-RAFT agent. X-ray photoelectron spectroscopy (XPS) characterization confirmed the presence of unreacted vinyl groups within the obtained block copolymer nanoparticles, providing a landscape for further functionalization via thiol-ene chemistry. Finally, the obtained block copolymer nanoparticles were employed as additives to tune the mechanical properties of hydrogels. We expect that this study not only offers considerable opportunities for the preparation of well-defined cross-linked block copolymer nanoparticles, but also provides important insights into the controlled polymerization of multivinyl monomers.

Hydrogel-based articular cartilage replacement materials are promising candidates for their potential to provide both high load-bearing capacity and low friction performance, similar to natural cartilage. Nevertheless, the design of these materials presents a significant challenge in reconciling the conflicting demands of the load-bearing capacity and lubrication. Despite extensive research in this area, there is still room for improvement in the creation of hydrogel-based materials that effectively meet these demands. Herein, a facile strategy is provided to realize simultaneously high load-bearing and low friction properties on the proposed hydrogel by modifying the surface of mechanically strong annealled PVA-PAAc hydrogel with a high hydration potential PAAm-co-PAMPS microgel. Consequently, a bilayer hydrogel with a porous surface and a compact substrate has been obtained. Compressive experiments confirmed that the bilayer hydrogel exhibited excellent mechanical strength with a compressive strength of 32.23 MPa at 90% strain. A high load-bearing (applied load up to 30 N), extremely low friction coefficiency (0.01-0.05) and excellent wear resistance (COF low to 0.03 after a 4 h test at 10 N using a steel ball as the contact pair) are successfully achieved. These findings provide new perspectives for the design of articular cartilage materials.

A cyclic ketene acetal (CKA) derived from d-glucal was synthesized, and its polymerization using free radicals has been investigated. NMR analysis of the resulting polymers revealed the formation of polyacetal-polyester copolymers, with up to 78% of ester linkages formed by radical ring-opening polymerization (rROP). Conversely, the polymerization of the monomer-saturated analogue only produced acetal linkages, demonstrating that the alkene functionality within the d-glucal pyranose ring is essential to promote ring-opening and ester formation, likely via the stabilization of an allyl radical. The thermal properties of the polymers were linked to the ratio of the ester and acetal linkages. Copolymerization with methyl methacrylate (MMA) afforded statistically PMMA-rich copolymers (66-98%) with linkages prone to hydrolytic degradation and decreased glass-transition temperatures. The retention of the pseudoglucal alkene function offers opportunities to functionalize further these bioderived (co)polymers.

We report a rapid cross-linking strategy for the fabrication of polymer hydrogels based on a thiol-disulfide cascade reaction. Specifically, thiolated polymers (e.g., poly(ethylene glycol), hyaluronic acid, sodium alginate, poly(acrylic acid), and poly(methylacrylic acid)) can be cross-linked via the trigger of Ellman's reagent, resulting in the rapid formation of hydrogels over 20-fold faster than that via the oxidation in air. The gelation kinetics of hydrogels can be tuned by varying the polymer concentration and the molar ratio of Ellman's reagent and free thiols. The obtained hydrogels can be further functionalized with functional moieties (e.g., targeting ligands) for the selective adhesion of cells. This approach is applicable to various natural and synthetic polymers for the assembly of hydrogels with a minimized gelation time, which is promising for various biological applications.

Dispersity (Đ) as a critical parameter indicates the level of uniformity of the polymer molar mass or chain length. In the past several decades, the development of explicit equations for calculating Đ experiences a continual revolution. This viewpoint tracks the historical evolution of the explicit equations from living to reversible-deactivation polymerization systems. Emphasis is laid on displaying the charm of explicit Đ equations in batch reversible-deactivation radical polymerization (RDRP), with highlights of the relevant elegant mathematical manipulations. Some representative emerging applications enabled by the existing explicit equations are shown, involving nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer (RAFT) polymerization systems. Stemming from the several outlined challenges and outlooks, sustained concerns about the explicit Đ equations are still highly deserved. It is expected that these equations will continue to play an important role not only in traditional polymerization kinetic simulation and design of experiments but also in modern intelligent manufacturing of precision polymers and classroom education.

Dielectric polymers that exhibit high energy density Ue, low dielectric loss, and thermal resistance are ideal materials for next-generation electrical equipment. The most widely utilized approach to improving Ue involves augmenting the polarization through increasing the dielectric constant εr or the breakdown strength Eb. However, as a conflicting parameter, the dielectric loss also increases inevitably at the same time. In addition, due to the long-term work under a strong electric field or high potential, dielectric materials often produce electrical damage (electrical tree), which is one of the main factors affecting the reliability and service life of electrical equipment. To address these problems, we herein develop dynamic cross-linked polyethylene materials (PE-MA-Epo) by polyethylene-graft-maleic anhydride (PE-MA) and polar epoxy monomers, which showed high εr (>7), low dielectric loss (<0.02), high Ue (5.16 J/cm3 at 425 MV/m), and outstanding discharge efficiency (97%). The performances of the materials are adequate to rival biaxially oriented polypropylene (BOPP) films. Moreover, the excellent self-healing capability of PE-MA-Epo enables the total recovery of εr and tan δ after electrical tree healing. After two cycles of electrical breakdown healing, Eb remained at 80%, which improves the durability and reliability of dielectric polymers. Therefore, PE-MA-Epo shows great potential for applications in advanced electronic power devices.

With synthetic ease and tunable degradation lifetimes, poly(β-amino ester)s (PBAEs) have found use in increasingly diverse applications, from gene therapy to thermosets. Protonatable amines in each repeating unit impart pH-dependent solution behavior and lifetimes, with acidic conditions favoring solubility, yet slowing hydrolysis. Due in part to these interconnected phenomena governing pH-dependent PBAE degradation, predictive degradation models, which would enable user-defined lifetimes, remain elusive. To separate the effects of charge state and solution pH on PBAE degradation, we synthesized poly(β-quaternary ammonium ester)s (PBQAEs), which differ from their parent PBAEs only by an additional methyl group, generating polymers with pH-independent cationic charge. Like PBAEs, PBQAE hydrolysis accelerates with increasing pH, although at a given pH, PBAE degradation outpaces PBQAE degradation. This difference is more pronounced in basic solutions, suggesting that deprotonated PBAE amines accelerate hydrolysis, providing an additional tuning parameter to PBAE lifetime and informing the degradation of PBAEs and other pH-responsive polymers.

Synthesis of high molecular weight polyesters prepared by acyclic diene metathesis (ADMET) polymerization of bis(undec-10-enoate) with isosorbide (M1), isomannide (M2), and 1,3-propanediol (M3) and the subsequent hydrogenation have been achieved by using a molybdenum-alkylidene catalyst. The resultant polymers (P1) prepared by the ADMET polymerization of M1 (in toluene at 25 °C) possessed high Mn values (Mn = 44400-49400 g/mol), and no significant differences in the Mn values and the PDI (Mw/Mn) values were observed in the samples after the hydrogenation. Both the tensile strength and the elongation at break in the hydrogenated polymers from M1 (HP1) increased upon increasing the molar mass, and the sample with an Mn value of 48200 exhibited better tensile properties (tensile strength of 39.7 MPa, elongation at break of 436%) than conventional polyethylene, polypropylene, as well as polyester containing C18 alkyl chains. The tensile properties were affected by the diol segment employed, whereas HP2 showed a similar property to HP1.

Stimulus-responsive polymer materials are an attractive alternative to conventional supramolecular and polymer assemblies for applications in sensing, imaging, and drug-delivery systems. Herein, we synthesized a series of pyrene-labeled α- and ε-poly-l-lysine conjugates with varying degrees of substitution (DSs). Hydrostatic-pressure-UV/vis, fluorescence, and excitation spectroscopies and fluorescence lifetime measurements revealed ground-state conformers and excited-state ensembles emitting fluorescence with variable intensities. The polylysine-based chemosensors demonstrated diverse ratiometric responses to hydrostatic pressure through adjustments in polar solvents, DSs, and polymer backbones. Additionally, the fluorescence chemosensor exhibited a promising glum value of 3.2 × 10-3, indicating potential applications in chiral fluorescent materials. This study offers valuable insights into the development of smart hydrostatic-pressure-responsive polymer materials.

The scaling relationship of complex coacervate core micelles (C3Ms) has been investigated experimentally and theoretically. The C3Ms are formed by mixing two oppositely charged block copolyelectrolyte solutions (i.e., AB + AC system) and are characterized by small-angle neutron (SANS) and X-ray scattering (SAXS). Scaling relationships for micellar structure parameters, including core radius, total radius, corona thickness, and aggregation number, all with respect to the core block length, are determined. A scaling theory is also proposed by minimizing the free energy per chain, leading to four regimes depending on the core and corona chain conformations. Although the corona block is significantly longer than the core block, the structure of our C3Ms is consistent with that of the crew-cut I regime. A highly swollen core by water enables the core blocks to be stretched significantly and corona chains to be minimally overlapped.