Search Results (221)

Because of their potential “smart” applications, multifunctional stimuli-responsive polymers are gaining increasing scientific interest. The present work explores the possibility of developing such materials based on the hydrolytically stable N-3-dimethylamino propyl methacrylamide), DMAPMA. To this end, the properties in aqueous solution of the homopolymer PDMAPMA and copolymers P(DMAPMA-co-MMA_x) of DMAPMA with the hydrophobic monomer methyl methacrylate, MMA, were explored. Two copolymers were prepared with a molar content x = 20% and 35%, as determined by Proton Nuclear Magnetic Resonance (¹H NMR). Turbidimetry studies revealed that, in contrast to the homopolymer exhibiting a lower critical solution temperature (LCST) behavior only at pH 14 in the absence of salt, the LCST of the copolymers covers a wider pH range (pH > 8.5) and can be tuned within the whole temperature range studied (from room temperature up to ~70 °C) through the use of salt. The copolymers self-assemble in water above a critical aggregation Concentration (CAC), as determined by Nile Red probing, and form nanostructures with a size of ~15 nm (for P(DMAPMA-co-MMA₃₅)), as revealed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The combination of turbidimetry with ¹H NMR and automatic total organic carbon/total nitrogen (TOC/TN) results revealed the potential of the copolymers as visual CO₂ sensors. Finally, the alkylation of the copolymers with dodecyl groups lead to cationic amphiphilic materials with an order of magnitude lower CAC (as compared to the unmodified precursor), effectively stabilized in water as larger aggregates (~200 nm) over a wide temperature range, due to their increased ζ potential (+15 mV). Such alkylated products show promising biocidal properties against microorganisms such as Escherichia coli and Staphylococcus aureus. Full article

This study focuses on the synthesis and characterization of a cationic ion-exchange sorbent derived from vermiculite and epoxy acrylate copolymers, designed to address freshwater scarcity by removing toxic metal ions from aqueous environments. The sorbent was engineered to preserve the chemical integrity of freshwater while adhering to environmental safety standards. Vermiculite served as the base material, modified with glycidyl methacrylate (GMA), acrylonitrile (ACN), and orthophosphoric acid (H₃PO₄) in a mass ratio of 1:0.35:0.15:3. Optimization experiments explored varying H₃PO₄ proportions (two- and threefold increases) to refine the synthesis conditions. The materials underwent microwave irradiation at 300 W for 10 min. Infrared (IR) spectroscopy confirmed the presence of functional groups (P=O, P−O−C), enhancing sorption capacity, while scanning electron microscopy (SEM) revealed a porous structure crucial for adsorption. Sorption properties, assessed via atomic emission spectroscopy, demonstrated capacities of 39.80 mg/g for MoO₄²⁻ and 39.06 mg/g for ReO₄⁻, with extraction efficiencies of 79% and 78%, respectively. Chemical stability tests indicated the sorbent retained up to 90% of its functionality in aggressive environments, highlighting its robustness. The developed sorbent offers a high-performance, cost-effective solution for heavy metal removal from wastewater, advancing sustainable water purification technologies. Full article

Reversible addition–fragmentation chain-transfer (RAFT) polymerization was used to synthesize novel thermoresponsive cationic molecular brushes with high yields—namely of copolymers of methoxyoligo(ethylene glycol) methacrylate, alkoxyoligo(ethylene glycol) methacrylate, and N-methacryloylaminopropyl-N,N-dimethyl-N-propylammonium bromide. Controlled polymerization yielded polymers with a molecular weight dispersity of ≤1.3 and conversions exceeding 80%. The influence of the cationic molecular brushes’ composition on their solubility in water and organic solvents, interfacial tension at the water–oil interface, and aggregation behavior in aqueous solutions was investigated. For the first time, we report the design of thermoresponsive cationic molecular brushes combining an antibacterial potential and tunable hydrophilic–hydrophobic properties, enabling highly precise control over their LCST behavior (17–68 °C) through composition tuning. The solubilization capacity of the hydrophobic compounds of brush micelles in water increased with the hydrophobic comonomer content. These polymers exhibited interfacial activity, significantly reducing the water–oil interfacial tension, with critical micelle concentrations (CMCs) of 3–10 mg/L. It was shown that the amphiphilic properties of the copolymers in aqueous solutions can be easily tuned in a desired direction by varying the content of the comonomer units. The obtained data indicate the potential of the polymers as micellar nanocarriers for controlled drug delivery. Full article

Designing conducting polymers with novel structures is essential for electrochemical energy storage devices. Here, copolymers of s-triazine and o-aminophenol are electropolymerized from an aqueous solution onto a carbon cloth substrate using the galvanostatic method. The poly(s-triazine-co-o-aminophenol) (PT-co-oAP) is characterized, and its charge storage properties are investigated in 1 M H₂SO₄ and in 1 M ZnSO₄. At 1 A g⁻¹, the specific capacities of PT-co-oAP reach 101.3 mAh g⁻¹ and 84.4 mAh g⁻¹ in 1 M H₂SO₄ and in 1 M ZnSO₄, respectively. The specific capacity of PT-co-oAP maintains 90.3% of its initial value after cycling at 10 A g⁻¹ for 2000 cycles in 1 M H₂SO₄. The high specific capacity achieved originates from abundant surface active sites, facile ion diffusion, with optimized active site structure achieved by forming copolymer. The charge storage mechanism involves the redox processes of amino/imino groups and hydroxyl/carbonyl groups in the copolymer, together with the insertion of cations. Two electrode devices using two PT-co-oAP and aqueous 1 M H₂SO₄ are assembled, and the maximum energy density reaches 63 Wh kg⁻¹ at 0.5 A g⁻¹ with a power density of 540 W kg⁻¹. The capacity retention of the device after 3000 cycles at 10 A g⁻¹ reaches 81.2%. Full article

Chiral molecules are integral to various biological and artificial systems, influencing processes from chemical production to optical activities. In this study, we explore the potential of chiral vinyl[2.2]paracyclophane (vinyl-PCP) as a monomer for the synthesis of homopolymers and copolymers with styrene. We achieved polymerization through anionic, cationic, and radical methods. The resulting polymers demonstrated significant chiral properties, even in copolymers with small fractions of the chiral monomer. Further, we developed a polymerizable vinyl emitter from 10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine (DMAC-TRZ) through a two-step synthesis with an overall yield of 48%. Copolymerization with chiral vinyl-PCP resulted in emissive polymers that demonstrated circularly polarized luminescence (CPL) properties. The inclusion of the chiral PCP monomer, acting both as a host material and the source of chirality for CPL, enhanced the photoluminescence quantum yield (PLQY) to 47.2% in N₂ at 5–10% emitter content, compared to 26.8% for the pure emitter polymer. CPL-active polymers show clear mirror-image Cotton effects at 240 nm and 267 nm and dissymmetry factors around +2 × 10⁻⁴ and −1 × 10⁻⁴. This self-hosting effect of PCP monomers underscores the potential of chiral vinyl-PCP for advanced functional materials in optical communication and bio-responsive imaging. Full article

Mechanically improved polymeric membranes with high ionic conductivity (IC) and good permeability are highly desired for next-generation anion exchange membranes (AEMs) in order to reduce Ohmic losses and enhance water management in alkaline membrane fuel cells. To move towards the fabrication of such high-performance membranes, the creation of hydrophilic ion-conducting double gyroid (DG) nanochannels within block copolymer (BCP) AEMs is a promising approach. However, this attractive solution remains difficult to implement due to the complexity of constructing a well-developed ion-conducting DG morphology across the entire membrane thickness. To deal with this issue, water permeable polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) membranes with ion-conducting DG nanochannels were produced by combining a solvent vapor annealing (SVA) treatment with a methylation process. Here, the SVA treatment enabled the manufacture of DG-forming BCP AEMs while the methylation process allowed for the conversion of pyridine sites to N-methylpyridinium (NMP⁺) cations via a Menshutkin reaction. Following this SVA-methylation method, the IC value of water-permeable (~384 L h⁻¹ m⁻² bar⁻¹) DG-structured BCP AEMs in their OH⁻counter anion form was measured to be of ~2.8 mS.cm⁻¹ at 20 °C while a lower IC value was probed, under the same experimental conditions, from as-cast NMP⁺-containing analogs with a non-permeable disordered phase (~1.2 mS.cm⁻¹). Full article

Herein, anionic (sodium dodecylbenzene sulfonate, SDBS) and cationic (cetyltrimethylammonium bromide, CTAB) surfactants are involved in the synthesis of a poly(acrylic acid-co-acrylamide) copolymer, p(AA-co-AM), containing nanoceria (CeO₂). The physicochemical and optical properties of CTAB-CeO₂@p(AA-co-AM) and SDBS-CeO₂@p(AA-co-AM) nanocomposites can be studied using different techniques. The physicochemical properties of nanoceria-immobilized p(AA-co-AM) are significantly developed when handled with SDBS. Compared to the CTAB-CeO₂@p(AA-co-AM) nanocomposite, SDBS-CeO₂@p(AA-co-AM) exhibits pronounced negatively charged mesoporous surfaces with Corel reef-like morphology. SDBS-CeO₂@p(AA-co-AM) contains ceria nano-cubes of ~30 nm size, evenly dispersed along a copolymeric moiety, displaying narrower energy bandgap. The photocatalytic efficiency of this nanocomposite is performed in activating persulfate-ions (PS) under visible light irradiation, yielding reactive oxygen species that effectively treat dye wastewater. Advanced SDBS-CeO₂@p(AA-co-AM)/PS/Vis photocatalytic oxidation system possesses ~100% methylene blue degradation efficiency within 2 h for five consecutive purification-cycles with thorough mineralization performance. Such superior photo-degradability consults efficacious synergistic combinations gathering the nanocomposite, persulphate-ions, and visible light radiation, yielding an escalated synergy-index value (SI = 6) with intensive generation of reactive-oxidizing species (SO₄^•−/h⁺ synergistic ratio 1:5.6). Including anionic-surfactant molecules in the synthesis of metal-containing copolymer nanocomposites is indispensably profitable in the future for the treatment of industrial wastewater. Full article

Background/Objectives: The endosomal escape of lipid nanoparticles (LNPs) is crucial for efficient mRNA-based therapeutics. Here, we present a cationic polymeric micelle (cPM) as a safe and potent co-delivery system with enhanced endosomal escape capabilities. Methods: We synthesized a cationic and ampholytic di-block copolymer, poly (poly (ethylene glycol)_4-5 methacrylate_a-co-hexyl methacrylate_b)_X-b-poly(butyl methacrylate_c-co-dimethylaminoethyl methacrylate_d-co-propyl acrylate_e)_Y (p(PEG_4-5MA_a-co-HMA_b)_X-b-p(BMA_c-co-DMAEMA_d-co-PAA_e)_Y), via reversible addition–fragmentation chain transfer polymerization. The cPMs were then formulated using the synthesized polymer by the dispersion–diffusion method and characterized by dynamic light scattering (DLS) and cryo-transmission electron microscopy (CryoTEM). The membrane-destabilization activity of the cPMs was evaluated by a hemolysis assay. We performed an in vivo functional assay of firefly luciferase (Fluc) mRNA using two of the most commonly studied LNPs, SM102 LNP and Dlin-MC3-DMA LNPs. Results: With a particle size of 61.31 ± 0.68 nm and a zeta potential of 37.76 ± 2.18 mV, the cPMs exhibited a 2–3 times higher firefly luciferase signal at the injection site compared to the control groups without cPMs following intramuscular injection in mice, indicating the high potential of cPMs to enhance the endosomal escape efficiency of mRNA-LNPs. Conclusions: The developed cPM, with enhanced endosomal escape capabilities, presents a promising strategy to improve the expression efficiency of delivered mRNAs. This approach offers a novel alternative strategy with no modifications to the inherent properties of mRNA-LNPs, preventing any unforeseeable changes in formulation characteristics. Consequently, this polymer-based nanomaterial holds immense potential for clinical applications in mRNA-based vaccines. Full article

Biofilms are a well-known multifactorial virulence factor with a pivotal role in chronic bacterial infections. Their pathogenicity is determined by the combination of strain-specific mechanisms of virulence and the biofilm extracellular matrix (ECM) protecting the bacteria from the host immune defense and the action of antibacterials. The successful antibiofilm agents should combine antibacterial activity and good biocompatibility with the capacity to penetrate through the ECM. The objective of the study is the elaboration of biofilm-ECM-destructive drug delivery systems: mixed polymeric micelles (MPMs) based on a cationic poly(2-(dimethylamino)ethyl methacrylate)-b-poly(ε-caprolactone)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA₃₅-b-PCL₇₀-b-PDMAEMA₃₅) and a non-ionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO₁₀₀-b-PPO₆₅-b-PEO₁₀₀) triblock copolymers, loaded with ciprofloxacin or azithromycin. The MPMs were applied on 24 h pre-formed biofilms of Escherichia coli and Pseudomonas aeruginosa (laboratory strains and clinical isolates). The results showed that the MPMs were able to destruct the biofilms, and the viability experiments supported drug delivery. The biofilm response to the MPMs loaded with the two antibiotics revealed two distinct patterns of action. These were registered on the level of both bacterial cell-structural alterations (demonstrated by scanning electron microscopy) and the interaction with host tissues (ex vivo biofilm infection model on skin samples with tests on nitric oxide and interleukin (IL)-17A production). Full article

We introduce a novel concept in nucleic acid delivery based on the use of mixed polymeric micelles (MPMs) as platforms for the preparation of micelleplexes with DNA. MPMs were prepared by the co-assembly of a cationic copolymer, poly(1-(4-methylpiperazin-1-yl)-propenone)-b-poly(d,l-lactide), and nonionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) block copolymers. We hypothesize that by introducing nonionic entities incorporated into the mixed co-assembled structures, the mode and strength of DNA binding and DNA accessibility and release could be modulated. The systems were characterized in terms of size, surface potential, buffering capacity, and binding ability to investigate the influence of composition, in particular, the poly(ethylene oxide) chain length on the properties and structure of the MPMs. Endo–lysosomal conditions were simulated to follow the changes in fundamental parameters and behavior of the micelleplexes. The results were interpreted as reflecting the specific structure and composition of the corona and localization of DNA in the corona, predetermined by the poly(ethylene oxide) chain length. A favorable effect of the introduction of the nonionic block copolymer component in the MPMs and micelleplexes thereof was the enhancement of biocompatibility. The slight reduction of the transfection efficiency of the MPM-based micelleplexes compared to that of the single-component polymer micelles was attributed to the premature release of DNA from the MPM-based micelleplexes in the endo–lysosomal compartments. Full article

Here, we report a reprocessible, reusable, self-healing, and form-switching polymeric adsorbent for remediating fluorinated pollutants in water. The copolymer hydrogel is designed to contain fluorophilic segments and cationic segments to induce strong binding with perfluorinated pollutants. The sorption performance reveals rapid and quantitative removal of these pollutants, driven by the synergistic effect of fluorophilic and electrostatic interaction. Importantly, a disulfide-containing dynamic crosslinker plays a crucial role in imparting multifunctionality. This enables self-healing by the restoration of crosslinks at the cut surfaces by disulfide exchange reactions and allows for the repeated use of the adsorbent via multiple adsorption–desorption cycles. Furthermore, the adsorbent is reprocessible by cleaving the crosslinks to afford linear copolymers, which can be repolymerized into a hydrogel network on demand. Also, form-switching capability is showcased through the aqueous self-assembly of linear copolymers into a fluorinated micelle, serving as another form of adsorbent for pollutant removal. Full article

In recent years, ionic liquids (ILs) have served as potential solvents to dissolve organic, inorganic, and polymer materials. A copolymer (for example, Pluronic) can undergo self-organization by forming a micelle-like structure in pure IL medium, and its assembly depends upon the composition of IL. To evaluate the role of ILs, accurate coarse-grained (CG) modeling of IL is needed. Here, we modeled 1-ethyl-3-methylimidazolium dicyanamide ([EMIM][DCA]) ionic liquid (IL) using a CG framework. We optimized CG parameters for the [DCA]⁻ anion by tuning the non-bonded parameters and selecting different kinds of beads. The molecular density (ρ) and radial distribution function (RDF) of our CG model reveal a good agreement with the all-atom (AA) simulation data. We further validated our model by choosing another imidazolium-based cation. Our modified CG model for the anion shows compatibility with the cation and the obtained density matches well with the experimental data. The strategies for developing the CG model will provide a guideline for accurate modeling of new types of ILs. Our CG model will be useful in studying the micellization of non-ionic Pluronic in the [EMIM][DCA] IL medium. Full article

Poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL), two biodegradable and biocompatible polymers that are commonly used for biomedical applications, are, respectively, the result of the ring-opening polymerization of LA and ε-CL, cyclic esters, which can be produced according to several mechanisms (cationic, monomer-activated cationic, anionic, and coordination-insertion), except for L-lactide, which is polymerized only by anionic, cationic, or coordination-insertion polymerization. A series of well-defined PLLA-b-PCL block copolymers have been obtained starting from the same PLLA homopolymer, having a molar mass of 2500 g·mol⁻¹, and being synthesized by coordination-insertion in the presence of tin octoate. PCL blocks were obtained via a cationic-activated monomer mechanism to limit transesterification reactions, and their molar masses varied from 1800 to 18,500 g·mol⁻¹. The physicochemical properties of the copolymers were determined by ¹H NMR, SEC, and DSC. Moreover, a series of nanoparticles (NPs) were prepared starting from these polyester-based copolymers by an emulsification/evaporation method. The sizes of the obtained NPs varied between 140 and 150 nm, as a function of the molar mass of the copolymers. Monomodal distribution curves with PDI values under 0.1 were obtained by Dynamic Light Scattering (DLS) and their spherical shape was confirmed by TEM. The increase in the temperature from 25 to 37 °C induced only a very slight decrease in the NP sizes. The results obtained in this preliminary study indicate that NPs have a temperature stability, allowing us to consider their use as drug-loaded nanocarriers for biomedical applications. Full article

New homogeneous bilayer membranes with a thin anion-exchange layer have been developed based on the copolymer of N,N-diallyl-N,N-dimethylammonium chloride (DADMAC) and ethyl methacrylate (EMA) on the surface of a membrane substrate made from polyfluorosulfonic acid (PFSA). The overall and partial current–voltage characteristics, as well as external and internal diffusion-limiting currents, were theoretically and experimentally investigated. Parameters such as specific conductivity, sorption, and diffusion permeability of individual membrane layers were determined, along with effective transport numbers and specific permselectivity of the bilayer homogeneous membranes in mixed solutions of calcium chloride and sodium chloride. It was found that applying a thin anion-exchange layer of DADMAC and EMA to the homogeneous membrane allows for the creation of a charge-selective bilayer membrane with enhanced selectivity toward monovalent metal cations. The specific selectivity of the bilayer membrane for sodium cations increases more than 6-fold (from 0.8 to 4.8). Verification of the obtained experimental data was performed within a four-layer mathematical model with quasi-equilibrium boundary conditions for the diffusion layer (I)/modifying layer (II)/membrane substrate (III)/diffusion layer (IV) in ternary NaCl+CaCl₂ solutions. Full article

Lithium-ion batteries (LIBs) are essential in modern electronics, particularly in portable devices and electric vehicles. However, the limited design flexibility of current battery shapes constrains the development of custom-sized power sources for advanced applications like wearable electronics and medical devices. Additive manufacturing (AM), specifically Fused Filament Fabrication (FFF), presents a promising solution by enabling the creation of batteries with customized shapes. This study explores the use of novel poly(acrylonitrile-co-polyethylene glycol methyl ether acrylate) (poly(AN-co-PEGMEA)) copolymers as solid polymer electrolytes for lithium-ion batteries, optimized for 3D printing using FFF. The copolymers were synthesized with varying AN:PEGMEA ratios, and their physical, thermal, and electrochemical properties were systematically characterized. The study found that a poly(AN-co-PEGMEA) 6:1 copolymer ratio offers an optimal balance between printability and ionic conductivity. The successful extrusion of filaments and subsequent 3D printing of complex shapes demonstrate the potential of these materials for next-generation battery designs. The addition of succinonitrile (SCN) as a plasticizer significantly improved ionic conductivity and lithium cation transference numbers, making these copolymers viable for practical applications. This work highlights the potential of combining polymer chemistry with additive manufacturing to provide new opportunities in lithium-ion battery design and function. Full article