Zong-Quan Wu

The environmental persistence of synthetic polymers has reached crisis levels, with conventional degradation strategies struggling to reconcile material durability with end-of-life recyclability. This study proposes a molecular design strategy: dynamic hydrogen bonds impart mechanical strength and thermal stability, while post-polymerization modification unlocks ultrasound-triggered degradation of the mechanophore. By strategically integrating mechanophores via ring-opening metathesis polymerization (ROMP), we develop a mechanically triggered degradable polymer system exhibiting multifunctionality. This architecture demonstrates: (1) Incorporation of hydrogen-bonded crosslinkers significantly elevates the glass transition temperature (Tg) while dramatically enhancing mechanical robustness; (2) The amide bond in the lactam unit can be modified via post-polymerization to achieve a nearly quantitative functional group conversion, thereby effectively “unlocking” its ultrasonic degradability; (3) Degraded oligomers with specific functional end groups can be readily repolymerized to form high-molecular-weight polymers. This work establishes a framework for sustainable polymer design, where noncovalent design of the polymer enables simultaneous optimization of performance metrics and environmental compatibility.

Porous frameworks attract considerable attention in recent years. However, precisely tuning the pore-size in a single atom precision and introducing tailor-made functionalities remain formidable challenges. In contrast to the reported strategies involving the elongation of linker and node, and linker exchange for tuning the pore-size of porous frameworks, herein, a polymerization-active two-dimensional (2D) hexagonal framework was synthesized with bis(alkyne)-Pd(II) embedded in pore-wall. The bis(alkyne)-Pd(II) units of the frameworks initiate living insertion polymerization of C1 monomer isocyanide, leading to direct pore expansion of the frameworks while maintain the ordering and porosity of the 2D hexagonal pore structure. The pore-size increased linearly and proportionally to number of the inserted isocyanide molecule, e.g., the pore-size increased from 4.3 to 6.6, 9.6, and 15.0 nm after 10, 20, 30, and 40 isocyanides were inserted into each pore-wall. Through the uniform and orderly insertion of isocyanide molecule, the pore-aperture of the resultant frameworks was controlled in a single-atom precision just by control over the number of the inserted isocyanide. Moreover, by inserting functional isocyanides, frameworks bearing tailored functionalities could be facilely achieved simultaneously with pore-expansion. The achieved pore-expanded frameworks with uniform pore structures were clearly demonstrated by synchrotron small-angle X-ray scattering (SAXS), nitrogen adsorption and desorption analysis, and directly high-resolution transmission electron microscope (HR-TEM) observations. Such porous frameworks with single-atom precisely controlled pore-size are ideal porous materials for nanomaterials fractionation and enzyme immobilization. Moreover, the embedded Pd(II)-complex in pore-expanded frameworks could be facilely removed through reductive elimination aided by the bidentate phosphine ligand, thereby transfer to more stable covalent polymer frameworks (CPFms) while maintained the ordering porous structure and integrity. This work provides not only a family of porous frameworks with the pore-size span from micro to meso and macro levels and a unprecedent strategy for controlled synthesis of porous frameworks with tailored structures and functions.

Electrochromic materials have attracted extensive attention due to their ability to achieve rapid and reversible regulation of optical properties under low-voltage driving.

Helical structure is one of the common structures in many natural macromolecules such as DNA and protein. In order to mimic the structures and functions of chiral nanoarchitectures in nature, various chiral nanomaterials generated from artificial helical polymers are fabricated successfully. This review comprehensively summarizes recent advances in chiral nanomaterials derived from helical polymers, focusing on their controlled formation, distinctive properties, and diverse applications. Helical polymers, such as polyacetylenes, polyisocyanides, and polycarbenes, serve as versatile building blocks for constructing well-defined chiral nanostructures through strategies including noncovalent interactions, covalent interactions, template-directed synthesis, and light-induced synthesis. These nanomaterials exhibit unique chiroptical, enantioselective, and stimuli-responsive characteristics, enabling their applications in circularly polarized luminescence (CPL), chiral separation and recognition, asymmetric catalysis, and targeted drug delivery. The precise control over helical conformation and supramolecular organization allows for tailored functionality and enhanced performance in technological and biomedical contexts. By integrating recent advances in synthetic strategies, property modulation, and applications, this review elucidates structure–property relationships and offers insights into the rational design of helical polymer-based chiral nanomaterials.

A one-pot living block copolymerization strategy was developed for well-defined PS- b -PPI. The resulting polymers exhibit polymerization-induced chiral self-assembly, excellent CPL performance and outstanding enantioseparation performance.

Helical structures such as DNA and proteins are indispensable in organism. As a distinctive structural configuration, helical structures hold extensive application potential across multiple fields. So, the research of helical macromolecules can help to deeply understand life phenomena and develop new materials for biomedical applications. This paper provides studies of some concise and typical helical macromolecules including natural helical polymers and synthesized helical polymers. The natural helical polymers, we mainly discuss the helical polysaccharides, DNA derivatives, helical peptide derivatives and synthesized helical polymers we mainly discuss polyisocynides. This review summarizes the applications of helical polymers in disease treatment, such as antibacterial therapy, delivery systems, and tissue repair. Moreover, the review also discusses the formation of helical polymers. Finally, current challenges and future perspectives for helical polymers into biomedical materials are also being addressed.

One-handed helical polyisocyanides bearing achiral benzoic acid pendants were readily synthesized via the asymmetric polymerization of achiral isocyanides using chiral Pd(II) catalysts. Despite the inexistence of any stereogenic centers, these polymers showed significant optical activity owing to their one-handed helicity. Two adjacent carboxyl groups on the polymer backbone coordinate with a single Cu²⁺, producing helical polyisocyanide–Cu complexes that act as highly active and recyclable chiral catalysts for asymmetric Diels–Alder and Michael addition reactions. Under optimized conditions, the block copolymer S-poly(3₅₀-b-2₃₀-b-3₅₀)/CuCl₂ delivers products in high yield (>77%) with outstanding stereocontrol (up to 98% ee). For Michael addition reactions, the same polymer gives up to 98% ee with yields >80%. Employing the enantiomeric backbone under the same conditions afforded the opposite R-configured product. Regulating the backbone helicity could control the direction of enantioselectivity and enantiomeric products could be facilely obtained using helical polyisocyanide with opposite handedness. Importantly, catalysts can be readily precipitated from the reaction mixture by addition of a poor solvent and reused for five consecutive cycles without significant loss of yield and enantioselectivity. After copper leaching and re-coordination, they can be cyclically applied to distinct asymmetric reactions.

Helices are ubiquitous in Nature and play indispensable roles in biological systems. A helix with an excess of one-handed helicity can be optically active because left- and right-handed helices are nonsuperimposable enantiomers. Stimulated by natural helices and their broad applications as chiral materials, artificial helical polymers have long been a hot research topic. Here, we describe recent advances in the controlled synthesis, structures, and functions of artificial helical polymers over the past decades. The main topics of this review include the controlled synthesis of one-handed static helical polymers through asymmetric polymerization and helix-sense-selective polymerization strategies and the precise fabrication of one-handed preferred dynamic helices via helix induction and memory. The remarkable progress in the applications of helical polymers in enantiomer separation, asymmetric catalysis, chiral self-assembly, and circularly polarized luminescence is then systematically summarized. Finally, the remaining challenges and future perspectives in the research areas of artificial helical polymers and related chiral materials are discussed.