Macromolecular Rapid Communications最新文献

Aromatic esters are amongst the oldest known chemical motifs that allow for thermal (re)processing of thermosetting polymers. Moreover, phenyl esters are generally known as activated esters that do not require a catalyst to undergo acyl transfer reactions. Even though dynamic aromatic esters find applications in commercialized thermoset formulations, all-aromatic esters have found limited use so far in the design of covalent adaptable networks (CAN) as a result of their high glass transition temperature (T_g) and specific curing process. Here, a strategy to include partly aromatic esters as dynamic cross-links inside low T_g (-40 °C) thermosetting formulations, using aliphatic esters derived from para-hydroxybenzoic acid, which serves as a highly activated phenol or as a reactive "phenylogous anhydride" is reported. A small molecule study shows that the activated phenyl ester bonds can readily exchange with free phenol moieties at 200 °C under catalyst-free conditions, while the addition of a catalyst allows for a faster exchange. Robust and hydrophobic polymer networks are conveniently prepared via rapid thiol-ene UV-curing of unsaturated phenol esters. The obtained networks show high thermal stability (350 °C), fast processability, good water resistance, and low creep up to 120 °C, thus showing good promise as a platform for CAN.

The covalent attachment of poly(ethylene glycol) (PEGylation) to materials minimizes non-specific fouling of the material surface with biocomponents. While the PEGylation reaction on polar surfaces is widely used and regarded as a common technique, the PEGylation on less polar polymers and elastomers is extremely difficult due to the absence of reactive points with PEG terminus. Herein, the design and synthesis of an orthogonal agent with a nitrile N-oxide and a phenyl carbamate that can mediate between an alkene and an amine are reported. The ligation capacity of the orthogonal agent is demonstrated through the model reaction to connect between 1-hexene and 4-methoxybenzylamine and the grafting reaction of PEG onto poly(styrene-co-butadiene) (SB) resin. The surface characteristics of PEGylated SB film are evaluated by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Because SB resin is frequently used as a 3D-printing polymer, the present study indicates that the orthogonal agent can be applicable to the surface modification of 3D-printed objects precisely manufactured by using a computer-aided design (CAD) file in the future.

In polymer science, mechanochemistry is emerging as a powerful tool for materials science and molecular synthesis, offering novel avenues for controlled polymerization and post-synthetic modification. Building upon the previous research, nitroxide-mediated polymerization (NMP) is merged with mechanochemistry through the design of nitroxide-based mechanophore macroinitiators, pioneering the first instance of a sonochemical nitroxide-mediated-type polymerization. As NMP usually requires high temperatures, this study demonstrates that a sonochemical NMP-type process allows polymerization under reduced temperatures down to 55 °C. Moreover, depending on the nature of the employed monomers, gelated networks are obtained, demonstrating the adaptability of the mechanophore system. This study elucidates the potential of mechanochemistry in polymer synthesis, offering insights into manipulating polymerization kinetics and advancing materials science applications.

A photo-assisted process is explored for improving the synthesis of oligo(triazole amide)s, which are prepared by solid phase synthesis using a repeated cycle of two reactions: amine-carboxylic acid coupling and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The improvement of the second reaction is investigated herein. A catalytic system involving Cu(II)Cl₂, N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA) and a titanocene photoinitiator is explored for reducing the reaction time of CuAAC. This catalyst is first tested on a model reaction involving phenylacetylene and ethyl azidoacetate in DMSO. The kinetics of these model experiments are monitored by ¹H NMR in the presence of different concentrations of the photoinitiator. It is found that 30 mol% of photoinitiator leads to quantitative reactions in only 8 min. These conditions are then applied to the solid phase synthesis of oligo(triazole amide)s, performed on a glycine-loaded Wang resin. The backbone of the oligomers is constructed using 6-heptynoic acid and 1-amino-11-azido-3,6,9-trioxaundecane as submonomers. Due to slow reagent diffusion, the CuAAC step required more time in the solid phase than in solution. Yet, one hour only is necessary to achieve quantitative CuAAC on the resin, which is twice as fast as previously-reported conditions. Using these optimized conditions, oligo(triazole amide)s of different length are prepared.

This comprehensive review addresses the self-healing phenomenon in perovskite solar cells (PSCs), emphasizing the reversible reactions of dynamic bonds as the pivotal mechanism. The crucial role of polymers in both enhancing the inherent properties of perovskite and inducing self-healing phenomena in grain boundaries of perovskite films are exhibited. The review initiates with an exploration of the various stability problems that PSCs encounter, underscoring the imperative to develop PSCs with extended lifespans capable of self-heal following damage from moisture and mechanical stress. Owing to the strong compatibility brought by polymer characteristics, many additive strategies can be employed in self-healing PSCs through artful molecular design. These strategies aim to limit ion migration, prevent moisture ingress, alleviate mechanical stress, and enhance charge carrier transport. By scrutinizing the conditions, efficiency, and types of self-healing behavior, the review encapsulates the principles of dynamic bonds in the polymers of self-healing PSCs. The meticulously designed polymers not only improve the lifespan of PSCs through the action of dynamic bonds but also enhance their environmental stability through functional groups. In addition, an outlook on self-healing PSCs is provided, offering strategic guidance for future research directions in this specialized area.

Antimicrobial peptides (AMPs) are promising alternatives to traditional antibiotics for treating skin wound infections. Nonetheless, their short half-life in biological environments restricts clinical applicability. Covalent immobilization of AMPs onto suitable substrates offers a comprehensive solution, creating contact-killing surfaces with long-term functionality. Here, a copolymer of poly[(hydroxy ethyl acrylamide)-co-(4-benzophenone acrylamide)-co-(pentafluorophenyl acrylate)-co-(ECOSURF EH-3 acrylate)], in short poly(HEAAm-co-BPAAm-co-PFPA-co-EH3A), is synthesized by free radical polymerization. Subsequent modification of active ester groups with the amine groups of SAAP-148, results in a copolymer, that is non-cytotoxic to human lung fibroblasts. UV photocrosslinking of the benzophenone units yields a polymer network that forms a hydrogel after swelling with aqueous medium. Both the SAAP-148-modified polymer in solution and the photocrosslinked hydrogels show good antimicrobial activity against strains of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii, including multidrug-resistant strains, frequently found in wound infections. The covalent attachment of SAAP-148 prevents leaching, ensuring sustained antimicrobial activity for at least 48 h in diluted human blood plasma and 14 days in PBS. This prolonged retention of antimicrobial activity in human blood plasma significantly enhances its clinical potential. Overall, this study shows the potential of the AMP-functionalized photocrosslinkable polymer as antimicrobial wound dressings, providing an effective alternative to antibiotics.

High-performance, versatile epoxy resins (EPs) are used in a variety of fields, but the manufacture of transparent, fireproof, and strong EPs remains a major challenge. The hyperbranched, multifunctional flame retardant (DSi) is prepared by using diethanolamine, polyformaldehyde, diphenylphosphine oxide, and phenyltrimethoxysilane as raw materials in this work. When the additional amount of DSi is only 2 wt.%, the EP-DSi₂ sample reaches a vertical burning (UL-94) V-0, and its limiting oxygen index (LOI) is 32.8%. When the content of DSi is 3 wt.%, the peak heat release rate (PHRR) and total smoke production (TSP) of EP-DSi samples are 43.8% and 21.4% lower than those of EP. The good compatibility of DSi and EP endows EP-DSi with high transparency, and the hyperbranched structure of DSi makes EP-DSi have obviously enhanced mechanical strength and toughness. The enhanced fire safety of EP-DSi is mainly due to the promoting carbonization and radical quenching effects of DSi. This paper offers a comprehensive design concept aimed at creating high-performance epoxy resins with good optical, mechanical, and flame-retardant properties, which have broad application prospects.

Epoxy systems are essential in numerous industrial applications due to their exceptional mechanical properties, thermal stability, and chemical resistance. Yet, recycling epoxy networks and reinforcing materials in epoxy composites remains challenging, raising environmental concerns. The critical challenge is the recovery of well-defined molecules upon depolymerization. To address these issues, an innovative strategy is developed utilizing imine-containing secondary amine hardener (M1). The reaction of M1 with DGEBA produced high-performance epoxy thermoset P1, which exhibits Young's modulus of 2.18 GPa and tensile strength of 63.4 MPa, and excellent stability in neutral aqueous conditions. Upon carbon-fiber reinforcement, Young's modulus and tensile strength are significantly elevated to 10.99 GPa and 328.3 MPa, respectively. The reactive secondary amine functionalities enabled the tailored network to display a well-defined growth pattern, yielding only well-defined molecules and intact carbon fibers upon acidic depolymerization. Consequently, the recycled polymers retained properties identical to those of P1. Notably, it is discovered that despite the cross-linked nature of the epoxy networks, complete dissolution in dichloromethane facilitated straightforward solvent-based recycling, allowing the recovery of undamaged carbon fibers and an epoxy thermoset with properties matching the virgin material. Presented novel monomer design and approach showcased two important and efficient recycling options for epoxy systems.

Artificial light-harvesting systems (LHSs) are of growing interest for their potential in energy capture and conversion, but achieving efficient fluorescence in aqueous environments remains challenging. In this study, a novel tetraphenylethylene (TPE) derivative, TPEN, is synthesized and co-assembled with poly(sodium 4-styrenesulfonate) (PSS) to enhance its fluorescence via electrostatic interactions. The resulting PSS⊃TPEN network significantly increased blue emission, which is further harnessed by an energy-matched dye, 4,7-di(2-thienyl)benzo[2,1,3]thiadiazole (DBT), to produce an efficient LHS with yellow emission. Moreover, this system is successfully applied to develop color-tunable light-emitting diode (LED) devices. The findings demonstrate a cost-effective and environmentally friendly approach to designing tunable luminescent materials, with promising potential for future advancements in energy-efficient lighting technologies.

The copolymerization of two or more monomers produces polymeric materials with unique properties that cannot be achieved with homopolymers. However, precise control over the polymer sequence remains challenging because the sequence is determined by the inherent reactivity of comonomers. Therefore, only limited methods using modified monomers or supramolecular interactions are reported. In this study, the sequence control of acrylate-styrene copolymerization using multinuclear zinc complexes is reported. The copolymerization of the zinc acrylate complex with a polymeric sheet-like structure and styrene in benzene affords a copolymer with a higher content of acrylate triad than calculated for the statistical random model, whereas tetranuclear zinc acrylate (TZA) affords a copolymer with fewer adjacent acrylate sequences. The copolymer with a higher content of acrylate triad exhibits a lower glass transition temperature because of the higher mobility of the longer polystyrene segments. These results highlight the promise of multinuclear zinc acrylate complexes as monomers for sequence-controlled copolymerization.