Macromolecular Chemistry and Physics最新文献

Three synthetic routes, thermally initiated thiol-ene polyaddition, isocyanate-based polyaddition, and transurethanization, were compared for the synthesis of non-isocyanate poly(urethane)s (NIPUs). Relatively high molecular weight polymers (M_n up to 19 kg×mol⁻¹) were successfully achieved via thiol-ene coupling using α,ω-diene-functionalized carbamates and aliphatic dithiols as monomers under solvent-free conditions and dicumyl peroxide as a thermal initiator at a [SH]/[Ene] ratio of 1.05. Compared to conventional isocyanate and transurethanization methods, the thiol-ene approach demonstrated slightly higher molar mass and reduced formation of urea and carbonate byproducts, independent of the formulation prepared. Thermal and mechanical characterization revealed that NIPUs, especially the ones prepared via thiol-ene, exhibited thermal transitions, tensile strength, and elongation at break comparable to or superior to those of their isocyanate-based counterparts. Adhesive performance was further enhanced through a thermally activated thiol-ene reactive bonding strategy, where in situ polymerization at the substrate interface led to a fourfold increase in lap shear strength (8 MPa) compared to a thermoplastic hot-melt application (2 MPa). These findings highlight that thermally initiated thiol-ene polyaddition is promising for the synthesis of high-performance, isocyanate-free polyurethane materials with potential applications in coatings, adhesives, and thermoplastics.

The growing demand for high-performance consumer electronics and telecommunication devices has driven the development of advanced, efficient, and high-speed data storage solutions. While silicon-based technologies have long dominated the memory market, their physical and performance limitations have spurred interest in alternative materials. Ferroelectric materials, characterized by their ability to exhibit spontaneous and reversible polarization, have emerged as promising candidates for next-generation memory technologies. Among these, polyvinylidene fluoride (PVDF), an organic ferroelectric polymer, has gained attention due to its mechanical flexibility, lightweight nature, non-toxicity, scalability, and ease of fabrication. This review critically evaluates the ferroelectric properties of PVDF and its potential for memory and emerging applications. PVDF's molecular structure, fabrication techniques, and performance in conventional memory technologies, such as FeRAM and FeFETs, are assessed, alongside its limitations compared to inorganic ferroelectrics like lead zirconium titanate (PZT) and hafnium zirconium oxide (HZO). Beyond conventional memory, PVDF's applications in neuromorphic computing and sensing technologies are discussed, where its ferroelectric, piezoelectric, and pyroelectric properties enable artificial synaptic plasticity, real-time detection, and transient data storage. Additionally, PVDF-based composites are examined, highlighting their ability to overcome intrinsic limitations of pure PVDF through the integration of organic and inorganic fillers. While PVDF may not yet match the performance of inorganic ferroelectrics in traditional metrics such as polarization strength and cycle endurance, its versatility, flexibility, and scalability make it a compelling candidate for applications in flexible electronics, biomedical devices, and the Internet of Things (IoT). This review provides a comprehensive assessment of PVDF's role in advancing next-generation memory technologies and multifunctional electronic applications.

An artistic depiction comparing structure-property relationships in lignin-derivable and petroleum-derived non-isocyanate polyurethanes (NIPUs) with conventional polyurethanes (PUs), highlighting how methoxy substituents from lignin and hydroxyl-rich NIPU chemistry modulate performance to approach or exceed traditional PU benchmarks. More details can be found in the Research Article by LaShanda T. J. Korley and co-workers (DOI: 10.1002/macp.202500433).

Antimicrobial resistance is an increasingly serious problem causing a large burden on global public health. A fundamental solution would be the development of antimicrobial drugs that, unlike conventional antibiotics, do not cause resistance. Antimicrobial polymers (APs), which mimic natural host defense peptides, kill bacteria via membrane disruption, a mechanism that is sufficiently unspecific to not cause resistance. While the amphiphilic balance is a key parameter determining the activity of APs, it is strongly connected to polymer topology as well. While APs featuring a bottle brush architecture in combination with moderate amphiphilicity proved to be highly effective, we wanted to probe if bottle brushes with increased hydrophobicity and similar charge density (leading to enhanced amphiphilicity) follow the same trend. To our surprise, when the more hydrophobic tert-butyl acrylamide is used as a comonomer, this trend is reversed, with linear copolymers being highly selective and bottle brush copolymers showing limited activity and selectivity. Our data suggests that the reason for this is to be found in the differing self-assembly behavior of both topologies, with bottle brushes forming strong intramolecular associations, which limit membrane activity.

Cationic, core-crosslinked, fully hydrophilic nanogels are well suited for nucleic acid delivery. Here, we report on an improved synthesis strategy to generate these biodegradable nanoparticles by elegant protecting group chemistry. Polycarbonate-based nanocarriers degrade into non-toxic components at physiological conditions that are removed by standard metabolic processes, thus increasing biocompatibility. However, polycarbonate backbones are susceptible to premature degradation at comparatively harsh synthesis conditions. It was previously necessary to carefully tune reaction parameters when working with the aliphatic polycarbonates and integrating the biogenic amine spermine as a crosslinker. Now, the secondary amines of the crosslinker are converted into hydrophobic Boc-protected carbamates in a simple one-pot reaction with high yield. This non-charged and more hydrophobic linker molecule greatly reduces nanogel core hydrophilicity during synthesis and, thereby, avoids premature aliphatic polycarbonate backbone hydrolysis. The Boc protecting groups are then easily removed by slightly modifying the already established acidic aqueous purification process, affording high quantities of nanogel for loading with various interesting therapeutic polyanionic cargo.