ABSTRACT We report a strategy for fabricating ultra‐pure nanoparticles–hydrogel composites by combining low‐pressure plasma‐based magnetron sputtering onto liquids with subsequent free radical photopolymerization. In a first step, various photocurable host liquids were screened for vacuum compatibility, viscosity, and stability under plasma exposure, highlighting poly(ethylene glycol) methyl ether acrylate (PEGMEA) as the most suitable candidate. A copper target was accordingly sputtered by an argon plasma onto PEGMEA, yielding stable colloidal suspensions of monomodal copper oxide (CuO) nanoparticles with a radius of 1.23 ± 0.015 nm. Careful outgassing procedure and sputtering conditions are critical to prevent undesired plasma‐induced reactions (e.g., premature polymerization). The total copper concentration was controlled by adjusting the deposition time and sputtering power during sputtering. Further addition of polyethylene glycol diacrylate crosslinker and diphenyl(2,4,6‐trimethylbenzoyl)phosphine oxide photoinitiator into the CuO NPs–PEGMEA colloids enables ex situ near‐UV photopolymerization to form transparent nanoparticles‐hydrogel composites. The composites contain small particles (7.38 ± 0.32 nm), and larger aggregates (67.47 ± 0.53 nm). Characterization by SEM, TEM, UV–vis spectrophotometry, photo‐rheology, and x‐ray absorption near‐edge spectroscopy confirmed the nanostructure and composition of the materials. This work opens new opportunities for developing surfactant‐free NP/hydrogel composites compatible with manufacturing techniques such as 3D printing.
ABSTRACT A compelling strategy to integrate contact‐active, non‐leaching functionalities directly within the polyurethane (PU) backbone is the covalent incorporation of heterocyclic structures. To investigate the influence of triazole‐based molecular architecture on polyurethane properties, triazole‐based dihydrazide chain extenders bearing C8 and C12 pendant alkyl chains were synthesized via Cu(I)‐catalyzed azide‐alkyne cycloaddition and incorporated into thermoplastic polyurethanes (TPUs). Thermal analysis revealed composition‐dependent stability governed by the interplay of triazole incorporation, side‐chain length, hard‐segment content, and diisocyanate structure. Systematic variation of pendant alkyl chain length, polyol molar mass, diisocyanate structure, and NCO/OH ratio demonstrated that molecular architecture governs molar mass distribution, microphase separation, storage modulus, and glass transition behavior. Increasing hard‐segment content and hydrophobic triazole substituents progressively increased surface hydrophobicity, with water contact angles reaching approximately 115°. Antimicrobial evaluation against Escherichia coli (Gram‐negative), Staphylococcus aureus (Gram‐positive), and Candida albicans (fungal strain) demonstrated reduced microbial adhesion on triazole‐functionalized TPU surfaces despite the absence of diffusional antimicrobial activity, indicating non‐leaching, contact‐active antifouling behavior. Furthermore, an optimized formulation yielded a preliminary waterborne dispersion that formed mechanically robust free‐standing films, demonstrating the feasibility of future environmentally friendly waterborne polyurethane coating systems.
ABSTRACT Developing mechanically robust eutectogels with stable ionic conductivity in highly polar deep eutectic solvents (DESs) remains challenging due to strong solvation effects that weaken interpolymer interactions. Here, a P(MAA‐ co ‐NIPA)/Choline chloride–ethylene glycol (ChCl–EG) copolymer eutectogel is developed via one‐step photopolymerization, in which microphase separation and localized hydrophobic shielding synergistically stabilize interpolymer hydrogen bonding. The limited solubility of poly(N‐isopropylacrylamide) (PNIPA) in the DES induces phase separation, forming polymer‐rich domains that enrich carboxyl and amide groups and promote interchain hydrogen bonding. Meanwhile, the α‐methyl groups along the PMAA backbone create localized hydrophobic microenvironments that reduce solvent accessibility and suppress solvation screening, thereby stabilizing interpolymer complexation. This combined mechanism enables a balance between mechanical reinforcement and energy dissipation. As a result, the eutectogel exhibits high tensile strength (0.91 MPa), high toughness (3.11 MJ m −3 ), and large extensibility (721%), along with high optical transparency (∼90%). It also demonstrates tunable ionic conductivity (1.29 mS cm −1 at room temperature), wide temperature tolerance, self‐healing ability, and reliable strain‐sensing performance. This work provides a molecular‐level design strategy for stabilizing noncovalent interactions in highly polar media and offers insights into the development of robust and multifunctional soft ionic conductors.
ABSTRACT In this report, hydrogels were combined with silver nanoparticles to impart antibacterial properties, yielding robust materials that prevent bacterial infections while maintaining stimulus responsiveness. The antibacterial hydrogel was based on double‐network (DN) hydrogels and prepared via in situ reduction of silver nitrate to silver nanoparticles (AgNPs). The DN hydrogel consists of polyvinyl alcohol‐ co ‐glutaraldehyde and poly(acrylamide‐ co ‐sodium acrylate‐ co ‐N‐isopropylacrylamide), serving as the first and second networks, respectively. The FT‐IR, x‐ray diffraction, and TEM analysis revealed the successful incorporation of silver nanoparticles within the DN hydrogel. The stimulus responsiveness of these hydrogels was assessed through temperature‐ and pH‐dependent swelling, and their thermal properties were also evaluated. The antibacterial efficacy of AgNPs embedded in DN hydrogels was validated by optical density (OD 600 ) measurements in suspension culture, which confirmed significant growth inhibition of both Escherichia coli (Gram‐negative) and Staphylococcus aureus (Gram‐positive) bacteria. Interestingly, the assessment of antibacterial activity using an agar diffusion assay with silver nanoparticle‐loaded hydrogels also revealed excellent bacterial growth inhibition against both Escherichia coli and Staphylococcus aureus (p < 0.0001). Hydrogels also showed notable cytocompatibility. These findings highlight the potential of AgNPs‐embedded stimuli‐responsive DN nanocomposite hydrogels, which may serve as promising materials for various biomedical products that require an antibacterial microenvironment.
ABSTRACT Poly(ethylene oxide) (PEO) is one of the most widely used materials for solid polymer electrolytes (SPEs). However, the high crystallinity and low ionic transference numbers of conventional PEOs are hindering their utilization in lithium metal batteries, except at temperatures above the melting point of PEO at ca. 60°C. Different strategies have thus been examined over the years to decrease the crystallinity of PEO. Here, we use α,ω‐dihydroxy PEO of low molar mass and a diol containing an aromatic pyridine group as comonomers in a step‐growth polymerization with a diisocyanate to obtain statistical polyurethanes. SPEs are obtained by mixing the polyurethanes with different amounts of LiTFSI. We thoroughly characterize the different investigated combinations by differential scanning calorimetry to determine crystallinity, rheology to assess mechanical properties, and temperature‐dependent ionic conductivity, linear sweep voltammetry, and lithium‐ions transference number measurements to discriminate the best candidates for SPEs. We demonstrate that the statistical distribution of the comonomers in the PUs effectively decreases the crystallization degree of PEO segments, while the presence of urethanes and aromatic amine functional groups allows better transport of lithium ions.
ABSTRACT A novel polystyrene‐supported Salen‐cobalt(III) complex (PS‐Salen‐Co(III)‐OAc) is prepared via covalent immobilization onto functionalized polystyrene microspheres. The catalyst is comprehensively characterized by FT‐IR, XPS, SEM‐EDS, and ICP‐OES, confirming successful immobilization and preservation of the catalyst sites. This heterogeneous system is applied in the alternating copolymerization of carbon dioxide (CO 2 ) and propylene oxide (PO), achieving high polycarbonate yields (up to 76%), excellent chemoselectivity (up to 99%), and narrow molecular weight distributions in the presence of a chain transfer agent ( Ð as low as 1.04) under mild conditions (30°C, 500 psi). The introduction of 1,2‐propanediol as a chain transfer agent further enhances the control over molecular weights. However, catalyst reuse is hindered by substantial mass gain due to covalent grafting of the polycarbonate product onto the supporting polystyrene matrix via the surface hydroxyl groups. Attempts to mitigate this grafting through hydroxyl capping and reduction are partially effective. A degradation‐recycling strategy, based on controlled depolymerization of surface‐grafted polymer chains via a back‐biting mechanism, significantly reduces mass gain and restores catalytic activity in subsequent cycles. This study provides a practical and efficient platform for sustainable CO 2 utilization through regenerable heterogeneous catalysis.
ABSTRACT The development of biodegradable packaging from renewable resources has become a central focus for both academia and industry. Marine crustacean waste constitutes an abundant source of chitin for the production of sustainable packaging materials. However, designing chitosan‐based bioplastics that are simultaneously multifunctional, mechanically robust, water‐resistant, and environmentally compatible remains a significant challenge. Herein, we explore the use of cellulose nanocrystals (CNCs), chitosan nanocrystals (ChNCs), and lignin nanoparticles (LNPs), as reinforcement agents for violacein‐containing chitosan bioplastics. All nanofillers improved the dispersion of violacein within the chitosan matrix, with CNC markedly enhancing mechanical properties (tensile strength of 68 MPa), ChNC promoting antibacterial activity (significant reductions of ∼2.01 log(CFU/mL) for Staphylocossus aureus and ∼2.11 log(CFU/mL) for Esherichia coli ), and LNP imparting strong antioxidant properties (up to 57.7% antioxidant activity). Building on these findings, we next crafted ternary‐reinforced nanocomposite films incorporating all three nanofillers. The resulting holistic bioplastic, referred to as CS@Vio 3% ‐(CNC_ChNC_LNP)‐ f , exhibited a complementary combination of properties, with concurrent improvements in mechanical strength, antibacterial efficacy, and antioxidant activity. Beyond supporting circular economy principles through the valorization of bio‐based resources, this work provides a holistic strategy for designing high‐performance chitosan‐based packaging materials.
ABSTRACT The polymorphic supermolecular structure of semicrystalline polymers exerts a decisive influence on their macroscopic properties, which is particularly pronounced in polyamide systems dominated by hydrogen bonding. This paper collates the formation mechanisms, regulation strategies and structure‐property relationships between polymorphic structures and macroscopic properties of polyamide systems reported in recent years. The regulation methods for the polymorphic crystalline structure of polyamides, based on polymorphism and Brill transition behavior, are categorized into three types: chemical methods involving random copolymerization and block copolymerization; physical methods including polymer blending, nucleating agent incorporation and solution induction; and processing methods such as stretching, shear fields, temperature fields and their coupled fields. The comprehensive properties of polyamides, especially mechanical, thermal, barrier and optical properties, can be effectively tailored via the regulation of their crystalline structures. By systematically reviewing the existing research progress, this review aims to deepen the understanding of the evolution mechanism of polyamide polymorphism and provide novel insights for the development of high‐performance polyamide materials.
ABSTRACT Poly(2‐ethyl‐2‐oxazoline) (PEtOx) represents a versatile platform for developing supramolecular polymer systems. In this study, propargyl‐terminated PEtOx was synthesized via cationic ring‐opening polymerization and subsequently functionalized at the γ‐chain end with either adamantane or phenyl groups using thiol–yne click chemistry. Monoazide‐functionalized β‐cyclodextrin (β‐CD‐N 3 ) was then covalently conjugated to these polymers through Cu(I)‐catalyzed azide–alkyne cycloaddition. Comprehensive characterization by 1H NMR, NOESY NMR, FTIR, GPC, and MALDI‐TOF MS confirmed successful synthesis and precise end‐group modifications. Notably, 2D NOESY NMR spectroscopy provided direct evidence of supramolecular host–guest interactions between the adamantane moiety and the β‐CD cavity in the P1/CD conjugate, while no significant inclusion complexation was observed for the phenyl‐terminated counterpart (P2/CD), highlighting the critical influence of end‐group identity on supramolecular complexation behavior in PEtOx‐based systems. Overall, this work introduces a versatile strategy for designing supramolecular polymer architectures through end‐group engineering and cyclodextrin conjugation, offering new perspectives for advanced functional materials with tunable self‐assembly properties.
ABSTRACT Amphiphilic polymer co‐networks (APCNs) are a unique class of soft matter, combining hydrophilic and hydrophobic polymer segments within a permanently connected macromolecular network. This combination gives rise to dual swelling in polar and nonpolar solvents, leading to hierarchical microstructures and tunable physical properties. In this review, we summarize recent advances in the synthesis, architecture, and behavior of APCNs, with a focus on well‐defined model systems that provide quantitative insight into structure–property relationships. Covalent and electrostatic cross‐linking strategies are discussed alongside the resulting morphologies, domain sizes, and swelling‐dependent mechanical properties. Besides bulk properties, interfacial features are also considered. Model APCNs serve as a unifying framework for connecting macromolecular design, mesoscopic structure, and macroscopic behavior, offering a rational basis for designing functional soft materials with tailored swelling, transport, and mechanical characteristics.
ABSTRACT Vitrimers are a class of associative covalent adaptable networks characterized by dynamic bond exchange, which allows thermoset‐like materials to be reprocessed without loss of crosslink density. These materials generally exhibit two important thermal transitions: the glass transition temperature (T g ) and the topology freezing temperature (T v ). T v defines the transition from a traditional thermoset network behavior to a viscoelastic state capable of topological rearrangement. Conventional T v characterization typically relies on temperature‐dependent thermomechanical measurements, where applied forces could perturb polymer relaxation and dynamic bond exchange. Although stress‐free methods such as scattering and fluorescence sensing have been explored, they could be difficult to scale or extend to complex systems such as phase‐separated blends. This study generalizes ellipsometric characterization for identifying key thermal transitions in vitrimer thin films, phase‐separated vitrimer blends, and porous systems. Using model systems, we show that ellipsometric thickness measurements can resolve both T g and apparent T v in a single heating–cooling cycle. Notably, reducing the thickness of vitrimer thin films can significantly shift their T g while leaving T v largely unchanged, highlighting the distinct sensitivities of segmental mobility and bond‐exchange‐mediated topology rearrangement to confinement. These results establish ellipsometry as an external stress‐free method for characterizing apparent T v in heterogeneous and confined vitrimer systems.
ABSTRACT Iridium‐containing polysiloxanes were developed as advanced coatings for UV‐exposure detection, offering a straightforward alternative to conventional electronic sensors. Vinyl‐ and thiol‐containing polysiloxanes were cross‐linked under UV‐A irradiation at room‐temperature in the presence of various iridium‐containing polysiloxanes, resulting in luminescence quenching (QY < 1%) and enabling direct visual detection of UV exposure within 5–10 min using simple light sources such as a flashlight. The swelling measurements provided insight into the network architecture and confirmed successful cross‐linking of polymers. The resulting silicone materials exhibited thermal stability with T 5% values of 371°C–401°C (argon) and 330°C–355°C (air), representing an improvement over conventional silicone rubber. This approach offers a straightforward route to luminescent silicone coatings with versatile applications, including visual detection of unwanted UV exposure during storage of equipment and prevention of photodegradation and aging of sensitive compounds.
ABSTRACT Polyurethane (PU) consumption continues to increase, raising growing concerns related to waste and its environmental impact. Hence, efforts have been directed toward the development of recycling technologies capable of recovering raw materials in line with circular economy principles. Within this framework, acidolysis has emerged as an effective depolymerization route and has been extensively studied for the recycling of PU foams. However, despite its relevance, the application of acidolysis to thermoplastic PU (TPU) remains largely unexplored. This study addresses this gap by investigating the chemical recycling of TPU residues generated from the ceramic sector. The influence of temperature, reaction time, and PU/acid molar ratio on the acid value (AV), hydroxyl number (IOH), and molar mass () of the recycled polyol (RP) was evaluated, and the degradation mechanisms were examined through spectroscopy and chromatography analysis. Finally, the potential use of the RP is assessed through its incorporation into new TPU formulations, revealing its suitability for partial substitution of commercial polyol up to 20 wt.% without compromising key thermal and mechanical properties. Overall, this study broadens the scope of acidolysis to an underexplored PU waste stream and proposes a viable circular recycling route for TPU residues from the ceramics industry.
ABSTRACT The present study demonstrated the development of polyurethane (PU) nanocomposite coatings incorporating biobased cardanol‐modified alkyd polyol and MoS 2 nanoparticles. Initially, biobased cardanol diol was synthesized by ring‐opening of cardanol monoglycidyl ether. Thereafter, alkyd resin was produced from prepared cardanol diol by solution condensation polymerization. ATR‐FTIR and 1 H NMR spectroscopies were used for the polyol structure confirmation. Then, the polyol was converted to PU coatings by reacting it with isophorone diisocyanate (IPDI) and modified using a loading of changing percentages (0.5%, 1%, 2%, and 4%) of MoS 2 nanoparticles. The corrosion performance of the resulting coatings was studied using immersion and electrochemical methods. The results showed that increasing the concentration of MoS 2 nanoparticles enhanced the corrosion resistance of PU nanocomposite coatings. The uniform distribution of MoS 2 nanoparticles was observed in the coatings, as evidenced by optical microscopy and scanning electron microscopy (SEM). Thermal stability was investigated by thermogravimetric analyzer (TGA), which showed increased stability with increasing nanoparticle loading percentage. The nanocomposite coatings exhibited better adhesion, flexibility, hydrophobicity, and chemical resistance than the PU coating in the absence of nanoparticles and the uncoated sample (mild steel panel). The amorphous and hydrophobic natures of coatings were observed by X‐ray diffraction (XRD) and contact angle estimation, respectively.
ABSTRACT Amino acid‐based polyurethanes (PUs) belong to a versatile group of biomaterials with extensive applications. Their structure can be adjusted by modification of hard and soft segments, side groups, and chain extenders, allowing precise control over their behavior, performance, and degradation rates. Incorporating nature‐inspired amino acid derivatives into the structure enhances biocompatibility and makes them more susceptible to enzymatic and hydrolytic breakdown. Recent studies have revealed varied materials from durable elastomers to stimuli‐responsive nanoparticles. These moieties can be incorporated through typical or non‐isocyanate pathways (including polycondensation or polyaddition reactions). It demonstrates a significant potential of amino acids and their derivatives to be used as chain extenders or precursors during PU production, advancing the development of novel materials tailored to specific applications. This review comprehensively describes the preparation of conventional PU from amino acid‐based diisocyanates and/or aliphatic/aromatic chain extenders, as well as their non‐isocyanate alternatives. Significant emphasis is placed on the elucidation of structure‐property behaviors and discussion of the products' properties related to their potential applications.
ABSTRACT Here, we report for the first time the formation of unique self‐cracking films prepared by drop‐casting polymersomes self‐assembled from the block copolymer PEI‐b‐PPOZ, composed of polyethyleneimine (PEI) and poly(2‐phenyl‐2‐oxazoline) (PPOZ). Using optical and electron microscopy, we investigated the relation between the evolution of self‐cracking films with various substrate types and over time. We found that crack‐patterned films, interconnected by a dense, channel‐like network, are readily and efficiently generated during water evaporation under ambient conditions (20°C–27°C and 40%–50% RH). The concentration of polymersomes and the drying temperature of polymersome cast films have a significant impact on crack formation and crack density. Interestingly, the crack‐patterned films served as a catalytic template to promote the hydrolytic polycondensation of tetramethoxysilane (TMOS), resulting in silica‐coated films that preserve the original crack pattern. SEM observations before and after silica deposition confirmed that the crack films are composed of stacked spherical polymersomes. The resulting silica‐hybrid crack films exhibited enhanced solvent resistance, and the crack channels concentrated target materials via capillary effects when immersed in an aqueous solution of silver acetate. Moreover, deposition of gold on the cracked film by resistance heating evaporation afforded effectively a transparent conductive gold mesh with sheet resistance of 19.9 Ω/◻ and optical transparency of > 90%.
The removal of per- and polyfluoroalkyl substances (PFAS) from water is of utmost importance. Quaternized polyethyleneimine (qPEI) was shown to be an efficient PFAS adsorbent material. Here, synthesized qPEI is immobilized on a quartz crystal microbalance (QCM) substrate and the adsorption of different PFAS on the qPEI-coated surface is explored in detail. qPEI adsorbers prepared as films are used to explore the gravimetric uptake of selected perfluoroalkyl carboxylic acids (PFCAs), and perfluorobutanesulfonic acid (PFBS). The advantage of this QCM method is the in situ monitoring of the adsorbed quantity. The results reveal a clear dependence of the uptake amount on the fluorinated carbon chain length, following the trend PFNA > PFOA > PFHpA > PFHxA > PFBS, indicating stronger interaction and higher adsorption capacities for longer-chain PFAS. Vibrational spectroscopy provides more insights and verifies that, in addition to the ionic interaction, the PFAS-CF groups participate in the fluorospecific interactions at the adsorption. Overall, this study demonstrates the suitability of qPEI-based films for PFAS uptake investigations and highlights the importance of the molecular structure on the adsorption efficiency. Although the PFAS concentrations explored are significantly larger than the relevant environmental concentrations, this study supports the development of efficient, low-cost PFAS adsorbent materials.
ABSTRACT Plasma grafting of itaconic acid ontopolypropylene (PP) surface was carried out to investigate the nature of the graft‐initiating sites in the system. It has been observed that the grafting is initiated by three mechanisms: peroxy, alkoxy, and alkyl linkages. The relative contribution of the three routes shows that the alkoxy linkage plays a significant role in graft initiation. The investigations were carried out using different techniques, such as Energy‐ Dispersive X‐ray Spectroscopy (EDX) and X‐ray Photoelectron Spectroscopy (XPS), and the results support the findings., Although a small fraction of grafting was initiated by alkyl and peroxide linkages, the observations highlighted the prominence of the alkoxy route.. The study presents an interesting aspect of graft functionalization on polymeric materials to design the material surfaces for specific applications. Almost 68% of the grafts follow the hydroperoxide decomposition route, giving alkoxy linkage.
