Macromolecular Rapid Communications最新文献

Organic electrochemical transistors (OECTs) offer unique advantages for bioelectronic and neuromorphic applications. The development of n-type enhancement-mode devices is essential for creating complementary circuits and low-power, bidirectional bioelectronic platforms. However, progress in this area has been hindered by the challenges associated with processing suitable n-type polymers. Here, we present a nanoparticle-based processing strategy for the ladder polymer poly(benzimidazobenzophenanthroline) (BBL). This n-type mixed conductor is soluble only in strong acids, which hinders straightforward fabrication. BBL nanoparticles are obtained by reprecipitation with an anionic surfactant, and systematic analysis reveals a particle-number-controlled scaling law, in which surfactant concentration and the polymer-to-surfactant ratio govern stabilization. Films prepared from these dispersions further underscore the importance of nanoparticle assembly: spray-coating yields dense, interconnected networks with markedly higher electrochemical activity than the porous films obtained by the filtration-transfer method. The spray-coated BBL films operate in enhancement mode, exhibiting efficient switching in the subthreshold regime while remaining non-conductive at zero gate bias. This work establishes a scalable route to n-type enhancement-mode OECTs, thereby broadening the foundation for next-generation bioelectronic and neuromorphic systems.

Precise spatial confinement of enzymes at oil-water interfaces offers an elegant strategy to enhance biphasic catalysis yet achieving robust and recyclable interfacial assemblies remains challenging. Here, we introduce an amphiphilic polymeric Janus particle platform that enables lipases to preferentially localize at interfaces, thereby achieving efficient Pickering interfacial catalysis (PIC). Crosslinked poly(hydroxypropyl methacrylate) colloids bearing surface carboxylic acid groups were synthesized via RAFT-mediated heterogeneous copolymerization and further transformed into snowman-shaped Janus particles through seeded emulsion polymerization. The resulting amphiphilic Janus colloids possess distinct hydrophilic-hydrophobic domains that facilitate both enzyme anchoring and emulsion stabilization. Candida rugosa lipase (CRL) immobilized on these particles exhibited strong interfacial activity, achieving enhanced catalytic efficiency, thermal stability, and recyclability compared to free CRL. The present work suggests that enzyme immobilization on Janus colloids is a promising approach to advance next-generation PIC.

Achieving both high strength and reprocessability in a single plastics material remains a fundamental challenge. Herein, we report the design and synthesis of novel supramolecular polydiketoenamine (PDK) network materials that were synergistically dual crosslinked by both the dynamic diketoenamine bonds and supramolecular cross-links (hydrogen-bonded benzene-1,3,5-tricarboxamide units). As a result, the PDK films exhibited a well-balanced combination of mechanical robustness and dynamic adaptability, achieving a high tensile strength of up to ∼77.21 MPa along with outstanding thermal reshaping and self-healing capabilities. Remarkably, beyond serving as strong structural films, the PDK plastic film exhibited superior performance as solid-state adhesives for diverse substrates-glass, metal, ceramic-exhibiting an enhanced lap-shear strength (up to ∼23.51 MPa) and retaining over 90% of its performance on glass after multiple reprocessing cycles. This work provides a promising strategy of integrating supramolecular cross-links into covalent adaptive network to construct high-performance, reprocessable network polymers that bridge the gap between the robustness of thermosets and the reprocessability of the thermoplastics.

Liquid crystal elastomers (LCEs) are promising stimuli-responsive materials for applications in wearable devices, biomedical devices, and soft robotics owing to their thermotropic shape-changing behaviors. However, conventional LCEs exhibit high phase-transition temperatures, often exceeding 60°C, which limits their use in human-interfacing applications. Herein, we present body heat-responsive LCEs incorporating dynamic thiourea bonds. Body temperature actuation is achieved by introducing comonomers that weaken anisotropic intermolecular interactions among mesogens into these LCEs, while the dynamic thiourea bonds impart reprocessability to the cross-linked network. Systematic formulation study elucidates the influence of comonomer structure on the actuation performance and network malleability. Furthermore, the dynamic thiourea-based LCE demonstrates reprogrammability even at ambient temperature, enabling facile fabrication of mechanically programmed 3D structures. Finally, we showcase a bump-array actuator that reversibly changes its surface topography in response to body heat.

It is promising but challenging to prepare poly(amino acid)s that directly bond to alcohols, especially saccharides. Herein, we report a novel method for the controlled ring-opening polymerization (ROP) of sarcosine N-carboxyanhydride (Sar-NCA) quantitatively initiated by hydroxyl groups using lutetium triflate (Lu(OTf)₃) as catalyst. Lu(OTf)₃ is devised to slow down the propagation by reducing the nucleophilicity of the amino group on the propagating chain end, thus realizing quantitative initiation efficiency (IE) of alcohol. Polysarcosine (PSar) samples with controlled molecular weights (M_n = 2.2-12.7 kg/mol) and low dispersities (Đ = 1.11-1.15) are obtained and full IE of the hydroxyl group is realized. Kinetic studies reveal that the propagation rate of Sar-NCA is significantly decreased in the presence of Lu(OTf)₃. The addition of Lu(OTf)₃ converts the characteristic of alcohol-initiated ROP of Sar-NCA from "slow initiation and fast propagation" to "fast initiation and slow propagation" which is essential of the polymerization control. Density functional theory (DFT) calculations provide mechanistic insights that Lu(OTf)₃ is prone to coordinate with the propagating chain end species of secondary amino and carbamate groups in the form of five- or eight-membered rings and retards the propagation. PSar products bearing glucose or mannose ester end groups, analogs of glycoproteins, are successfully synthesized by applying this protocol. The obtained mannose-functionalized PSar shows significantly accelerated ingestion by cancer cells.

Polymer lipids (PLs) are an essential component for the stability of lipid nanoparticles (LNPs) for gene delivery. Poly(ethylene glycol) (PEG)-based lipids are the current gold standard. However, they are suspected to be responsible for rare adverse reactions to the LNP-based COVID-19 vaccines. Therefore, alternative PLs are being intensively investigated. A particularly promising alternative are poly(sarcosine) (PSar)-based lipids. However, one significant bottleneck of pSar-based biomaterials is the synthesis of the monomer sarcosine-N-carboxyanhydride (Sar-NCA). Current methods rely on highly toxic di- or triphosgene to obtain the monomer directly from the amino acid sarcosine. Herein, we present a phosgene-free, CO₂-based route to Sar-NCA in gram scale and excellent purity, suitable for the subsequent living polymerization to pSar. Furthermore, we used the obtained pSar for the synthesis of pSar lipids suitable for LNP preparation. Due to its low toxicity and simplicity, the CO₂-based Sar-NCA synthesis has great potential to become an attractive alternative to current monomer synthesis pathways.

Poly(ylide)s - Exploring a vast chemical space: In the Research Article (DOI: 10.1002/marc.202500641), Patrick Théato, Kevin Neumann, and co-workers introduce poly(iminopyridinium ylide) as a stable, charge-neutral and hydrophilic polymer that resists nonspecific biomolecular interactions and stabilizes proteins, positioning it as a promising material in medicine.

Geometric configuration of C═C bonds along the polymer backbone plays a crucial role in determining the physical properties of the resulting materials. However, the key role of cis/trans-C═C units in the crystallization and physical property of stereoisomeric polymers has not been well understood. Herein, we report a unique series of linear unsaturated polyesters, poly(butene succinate) (PBuS), with the precisely controlled cis/trans-C═C unit contents synthesized via melt polycondensation. High-molecular-weight cis/trans-polyesters without detectable isomerization or saturation of C═C bonds were prepared in the used polycondensation method. We find that the synthesized PBuS was crystallizable across the entire range of cis/trans unit ratios and showed the unique isodimorphic-like crystallization behavior, with an asymmetric pseudo-eutectic point at ∼31% cis-unit content. Notably, cis-PBuS crystallized much faster than its trans-counterpart, highlighting the profound effect of C═C isomerism on crystallization behavior. Mechanical properties of PBuS correlated strongly with the crystallinity and crystalline structure, showing low strength and modulus but high flexibility around the pseudo-eutectic composition. This work elucidates the crucial role of cis/trans isomerism in polymer crystallization and provides a rational way for designing the aliphatic polyesters with tailored physical properties.

We distinguish two rheological routes to the liquid-solid transition (LST) in soft materials by tracking the linear viscoelastic spectrum under small-amplitude oscillatory shear. Type I (dynamical arrest) shows the growth of a low-frequency elastic plateau without a reversal in the loss-tangent trend; Type II (percolation with criticality) features scale-free spectra at a well-defined time and a reversal in the loss-tangent trend. In synthetic hectorite suspensions spanning broad clay and salt concentrations, freshly prepared samples consistently follow Type II. After aging and pre-shear, the pathway becomes history-dependent: a map in composition-shear space reveals a boundary where high clay concentrations undergo Type I only, whereas lower clay concentrations evolve from Type I to Type II; increasing pre-shear rate shifts this boundary to higher clay content. A unified mechanism links these routes to aggregation kinetics: early particle-cluster growth yields peaked cluster-size distributions and Type I arrest; later depletion-enhanced cluster-cluster aggregation produces heavy-tailed distributions and Type II percolation. These results explain why "shear rejuvenation" does not restore the fresh state and provide a spectrum-based framework relevant to colloids and polymer systems undergoing physical or chemical gelation.