Search Results (108)

Multilayer and free-standing films self-assembled from water-soluble anionic azo dye acid yellow 9 (AY9) and both poly(allylamine hydrochloride) (PAH) and chitosan (CS) cationic polyelectrolytes were fabricated from water solution using a layer-by-layer (LbL) technique and characterized by UV–Vis and Raman spectroscopy. Observations were made of a strong, unexpected, and highly unusual colour change from deep red to a distinct dark blue upon exposure of the multilayer films to an acidic environment. The colour change was attributed to the multilayer films only and was not observed either for the polymer or the dye alone, or their mixture in water solution, nor when cast as free-standing films. The significant shift to blue colour of the absorption peaks was quantified with UV–Vis spectroscopy, and a proposed explanation is presented based on density functional theory (DFT) calculations exploring possible and most likely acid-base equilibria configurations of the azo dye that result from being self-assembled. Full article

Pathogenic bacterial infections pose serious health risks, underscoring the need for timely treatments. Manganese dioxide (MnO₂) nanoparticles (NPs) have attracted considerable attention owing to their outstanding chemical stability, favorable biocompatibility, high reactivity, and catalytic ability to decompose hydrogen peroxide, making them promising antibacterial agents. A clear understanding of their antibacterial mechanisms is essential for evaluating their therapeutic potential in clinical settings. In this study, MnO₂ NPs were synthesized by reacting potassium permanganate (KMnO₄) with poly(allylamine hydrochloride) (PAH), ensuring complete conversion to MnO₂ NPs. The resulting NPs were characterized for their physicochemical properties, and their antibacterial activity against E. coli and S. aureus was evaluated using growth curve assays and reactive oxygen species (ROS) quantification. Results indicated the killing efficiency of MnO₂ NPs increased with exposure time and concentration, reflecting high susceptibility of both bacterial strains. Scanning electron microscopy (SEM) analysis revealed that the interaction between MnO₂ NPs and bacterial cells caused significant disruption of cell wall integrity. This study provides a valuable platform for evaluating MnO₂ nanoparticles as antibacterial agents and for exploring their mechanisms in medical applications. Full article

Per- and polyfluoroalkyl substances (PFASs), used since the 1940s, are persistent and carcinogenic pollutants. Water is a major exposure route; effective removal is essential. While nanofiltration (NF) and reverse osmosis (RO) are effective but costly, ultrafiltration (UF) membranes offer advantages such as lower cost and higher flux, but their relatively large pore size makes them ineffective for PFAS compounds like perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Since PFAS removal depends on both pore size and surface properties, this study investigates the effect of polyelectrolyte multilayer coatings using poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) on the zeta potential of UF membranes. Pristine UF membranes showed limited performance (UP150: ~2% for both PFOS and PFOA; UP020: 34.4% PFOS, 24.1% PFOA), while coating significantly enhanced removal (coated UP150: 45.3% PFOS, 43.4% PFOA; coated UP020: 77.8% PFOS, 73.3% PFOA). The modified UF membranes achieved PFAS removal efficiencies significantly closer to NF membranes, though still below those of RO (e.g., BW30XLE: up to 91.0% PFOS, 88.3% PFOA; NP030: up to 81.0% PFOS, 79.3% PFOA). Findings emphasize the importance of membrane surface charge and suggest that modified UF membranes offer a promising, low-cost alternative for PFAS removal under low-pressure conditions. Full article

Network polymers with β-cyclodextrin moieties were prepared by nucleophilic substitution reactions between polyamines, linear polyethyleneimine (LPEI), polyallylamine (PAA), (ε-poly-L-lysine) (EPL), and monochlorotriazinyl-β-cyclodextrin (MCTCD) in methanol/water mixed solvent or water. The reactions under conditions of high material concentration (30 wt%) and a feed ratio of [MCT]/[NH] = 0.5 (mol/mol) successfully yield porous polymers via reaction-induced phase separation. The molecular structure of the polyamines and reaction conditions strongly affected the morphology of the resulting porous polymers. The porous polymers were composed of connected particles, gathered (slightly connected) particles, and/or disordered bulky structures, with sizes of 10⁻⁹ m–10⁻⁸ m. An increase in the molecular weight of LPEI and PAA and the feed molar ratio of [MCT]/[NH] tended to decrease the particle size. Young’s moduli of the LPEI-MCTCD and PAA-MCTCD porous polymers increased with an increase in bulk density, which was derived from small particle sizes. The wide particle size distribution and disordered structure caused collapse by the compression under 50 N of pressure. An LPEI-MCTCD adsorbed methyl orange, methylene blue, and phenolphthalein through ionic interactions, π–π interaction, and/or β-cyclodextrin inclusion. Full article

Loss of implant function is a common complication in orthopaedic and dental surgery. Among the primary causes of implant failure are peri-implant infections which often result in implant removal. This study demonstrates the development of a new antimicrobial titanium coating with ZnO nanoparticles of various sizes and morphologies immobilised in poly(allylamine hydrochloride) and alginate multilayers, combined with epitaxially grown vaterite crystals. The coated samples were characterised with various methods (FTIR, XRD, SEM) and surface properties were evaluated via water contact angle and surface charge measurements. Zinc ion release was quantified using ICP-MS. The antimicrobial efficacy of the coatings was tested against Staphylococcus aureus, Staphylococcus epidermidis, and Candida albicans while the biocompatibility was tested with preosteoblast cells (MC3T3-E1). Results demonstrated the successful preparation of a calcium carbonate/ZnO composite coating with epitaxially grown vaterite on titanium surfaces. The Zn ions released from ZnO nanoparticles dramatically influenced the morphology of vaterite where a new flower-like morphology was observed. The coated titanium surfaces exhibited robust antimicrobial activity, achieving over 90% microbial viability reduction for Staphylococcus aureus, Staphylococcus epidermidis, and Candida albicans. Importantly, the released Zn²⁺ concentrations remained below the cytotoxicity limit for MC3T3-E1 cells, showing potential for safe and effective implant applications. Full article

This study explores the layer-by-layer (LBL) modification of polyacrylonitrile (PAN) hollow fibers for effective Mg²⁺/Li⁺ separation. It employs an LBL method of surface modification using polyelectrolytes, specifically aiming to enhance ion selectivity and improve the efficiency of lithium extraction from brines or lithium battery wastes, which is critical for battery recycling and other industrial applications. The modification process involves coating the hydrolyzed PAN fibers with alternating layers of positively charged polyelectrolytes, such as poly(allylamine hydrochloride) (PAH), polyethyleneimine (PEI), or poly(diallyldimethylammonium chloride) (PDADMAC) and negatively charged polyelectrolytes, such as poly(styrene sulfonate) (PSS), to form polyelectrolyte multilayers (PEMs). This study evaluates the modified membranes in Mg²⁺ and Li⁺ salt solutions, demonstrating significant improvements in selectivity for Mg²⁺/Li⁺ separation. PAH was identified as the optimal positively charged polyelectrolyte. PAN hollow fibers modified with ten bilayers of PAH/PSS achieved rejection rates of 95.4% for Mg²⁺ ions and 34.8% for Li⁺ ions, and a permeance of 0.39 LMH/bar. This highlights the potential of LBL techniques for effectively addressing the challenges of ion separation across a variety of applications. Full article

More than half of the global population is unable to consume dairy products due to lactose intolerance (hypolactasia). Current enzyme replacement therapy methods are insufficiently effective as a therapeutic approach to treating lactose intolerance. The encapsulation of β-galactosidase in polyelectrolyte microcapsules by using the layer-by-layer method could be a possible solution to this problem. In this study, adsorption and co-precipitation methods were employed for encapsulating β-galactosidase in polyelectrolyte microcapsules composed of (polyallylamine /polystyrene sulphonate)₃. As a result, the co-precipitation method was chosen for β-galactosidase encapsulation. The adsorption method permits to encapsulate six times less enzyme compared with the co-precipitation method; the β-galactosidase encapsulated via the co-precipitation method released no more than 20% of the initially encapsulated enzyme in pH 2 or 1 M NaCl solutions. In contrast, when using the sorption method, about 100% of the initially encapsulated enzyme was released from the microcapsules under the conditions described above. The co-precipitation method effectively prevents the complete loss of enzyme activity after 2 h of incubation in a solution with pH 2 while also alleviating the adverse effects of ionic strength. Consequently, the encapsulated form of β-galactosidase shows promise as a potential therapeutic agent for enzyme replacement therapy in the treatment of hypolactasia. Full article

The layer-by-layer (LbL) assembling of oppositely charged polyelectrolytes was studied using semi-synthetic polysaccharide derivatives, namely the polycations 6-aminoethylamino-6-deoxy cellulose (ADC) and cellulose (2-(ethylamino)ethylcarbamate (CAEC), as well as the polyanion cellulose sulfate (CS). The synthetic polymers poly(allylamine) (PAH) and poly(styrene sulfonate) (PSS) were employed as well for comparison. The stepwise adsorption process was monitored by whispering gallery mode (WGM) experiments and zeta-potential measurements. Distinct differences between synthetic- and polysaccharide-based assemblies were observed in terms of the quantitative adsorption of mass and adsorption kinetics. The LbL-approach was used to prepare µm-sized capsules with the aid of porous and non-porous silica particle templates. The polysaccharide-based capsule showed a switchable permeability that was not observed for the synthetic polymer materials. At ambient pH values of 7, low-molecular dyes could penetrate the capsule wall while no permeation occurred at elevated pH values of 8. Finally, the preparation of protein-loaded LbL-capsules was studied using the combination of CAEC and CS. It was shown that high amounts of protein (streptavidin and ovomucoid) can be encapsulated and that no leaking or disintegration of the cargo macromolecules occurred during the preparation step. Based on this work, potential use in biomedical areas can be concluded, such as the encapsulation of bioactive compounds (e.g., pharmaceutical compounds, antibodies) for drug delivery or sensing purposes. Full article

An electrochemical sensor sensitive to coenzyme A (CoA) was designed using a CoA-responsive polyallylamine–manganese oxide–polymer dot nanogel coated on the electrode surface to detect various genetic models of osteoarthritis (OA). The CoA-responsive nanogel sensor responded to the abundance of CoA in OA, causing the breakage of MnO₂ in the nanogel, thereby changing the electroconductivity and fluorescence of the sensor. The CoA-responsive nanogel sensor was capable of detecting CoA depending on the treatment time and distinguishing the response towards different OA genetic models that contained different levels of CoA (wild type/WT, NudT7 knockout/N7KO, and Acot12 knockout/A12KO). The WT, N7KO, and A12KO had distinct resistances, which further increased as the incubation time were changed from 12 h (R_12h = 2.11, 2.40, and 2.68 MΩ, respectively) to 24 h (R_24h = 2.27, 2.59, and 2.92 MΩ, respectively) compared to the sensor without treatment (R_control = 1.63 MΩ). To simplify its application, the nanogel sensor was combined with a wireless monitoring device to allow the sensing data to be directly transmitted to a smartphone. Furthermore, OA-indicated anabolic (Acan) and catabolic (Adamts5) factor transcription levels in chondrocytes provided evidence regarding CoA and nanogel interactions. Thus, this sensor offers potential usage in simple and sensitive OA diagnostics. Full article

Bimetallic nanomaterials have generated significant interest across diverse scientific disciplines, due to their unique and tunable properties arising from the synergistic combination of two distinct metallic elements. This study presents a novel approach for synthesizing branched gold–platinum nanoparticles by utilizing poly(allylamine hydrochloride) (PAH)-stabilized branched gold nanoparticles, with a localized surface plasmon resonance (LSPR) response of around 1000 nm, as a template for platinum deposition. This approach allows precise control over nanoparticle size, the LSPR band, and the branching degree at an ambient temperature, without the need for high temperatures or organic solvents. The resulting AuPt branched nanoparticles not only demonstrate optical activity but also enhanced catalytic properties. To evaluate their catalytic potential, we compared the enzymatic capabilities of gold and gold–platinum nanoparticles by examining their peroxidase-like activity in the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). Our findings revealed that the incorporation of platinum onto the gold surface substantially enhanced the catalytic efficiency, highlighting the potential of these bimetallic nanoparticles in catalytic applications. Full article

We present the construction of an organic electrochemical transistor (OECT) based on poly(3,4-ethylendioxythiophene, PEDOT) and polyallylamine (PAH) and its evaluation as a bioelectronic platform for urease integration and urea sensing. The OECT channel was fabricated in a one-step procedure using chemical polymerization. Then, urease was immobilized on the surface by electrostatic interaction of the negatively charged enzyme at neutral pH with the positively charged surface of PEDOH-PAH channels. The real-time monitoring of the urease adsorption process was achieved by registering the changes on the drain–source current of the OECT upon continuous scan of the gate potential during enzyme deposition with high sensitivity. On the other hand, integrating urease enabled urea sensing through the transistor response changes resulting from local pH variation as a consequence of enzymatic catalysis. The response of direct enzyme adsorption is compared with layer-by-layer integration using polyethylenimine. Integrating a polyelectrolyte over the adsorbed enzyme resulted in a more stable response, allowing for the sensing of urine even from diluted urine samples. These results demonstrate the potential of integrating enzymes into the active channels of OECTs for the development of biosensors based on local pH changes. Full article

Polyelectrolyte microcapsules (PMC) based on polyallylamine and polystyrene sulfonate are utilized in various fields of human activity, including medicine, textiles, and the food industry, among others. However, characteristics such as microcapsule size, shell thickness, and pore size are not sufficiently studied and systematized, even though they determine the possibility of using microcapsules in applied tasks. The aim of this review is to identify general patterns and gaps in the study of the morphology of polyelectrolyte microcapsules obtained by the alternate adsorption of polystyrene sulfonate and polyallylamine on different solid cores. First and foremost, it was found that the morphological change in polyelectrolyte microcapsules formed on different cores exhibits a significant difference in response to varying stimuli. Factors such as ionic strength, the acidity of the medium, and temperature have different effects on the size of the microcapsules, the thickness of their shells, and the number and size of their pores. At present, the morphology of the microcapsules formed on the melamine formaldehyde core has been most studied, while the morphology of microcapsules formed on other types of cores is scarcely studied. In addition, modern methods of nanoscale system analysis will allow for an objective assessment of PMC characteristics and provide a fresh perspective on the subject of research. Full article

As the atmospheric carbon dioxide (CO₂) concentration rapidly rises, carbon capture, utilization, and storage (CCUS) is an emerging field for climate change mitigation. Various carbon capture technologies are in development with the help of adsorbents, membranes, solvent-based systems, etc. One of the main challenges in this field is the removal of CO₂ from nitrogen (N₂) gas. This paper focuses on mixed matrix membrane technology, for which the CO₂/N₂ separation performance is based on differences in gas permeations. Membrane separation and purification technologies are widely studied for carbon capture. Microporous adsorbents such as zeolites and metal organic frameworks (MOFs) for carbon capture have been attracting researchers’ attention due to their highly porous structures, high selectivity values, and tunable porosities. Utilizing microporous adsorbents dispersed within a novel, blended polymer matrix, fourteen membranes were prepared with the commercial MOF ZIF-8, zeolite 13X, and kaolin, with methyl cellulose (MC) and polyvinyl alcohol (PVA), which were tested using a single gas permeation setup in this study. The addition of polyallylamine (PAH) as a chemisorbent was also investigated. These membranes were synthesized both with and without a polyacrylonitrile (PAN) support to compare their performances. MC was found to be an ideal polymeric matrix component to develop free-standing MMMs. At 24 °C and a relatively low feed pressure of 2.36 atm, a free-standing zeolite-13X-based membrane (MC/PAH/13X/PVA) exhibited the highest N₂/CO₂ selectivity of 2.8, with a very high N₂ permeability of 6.9 × 10⁷ Barrer. Upon the optimization of active layer thickness and filler weight percentages, this easily fabricated free-standing MMM made of readily available materials is a promising candidate for CO₂ purification through nitrogen removal. Full article

In healthcare facilities, infections caused by Staphylococcus aureus (S. aureus) from textile materials are a cause for concern, and nanomaterials are one of the solutions; however, their impact on safety and biocompatibility with the human body must not be neglected. This study aimed to develop a novel multilayer coating with poly(allylamine hydrochloride) (PAH) and immobilized ZnO nanoparticles (ZnO NPs) to make efficient antibacterial and biocompatible cotton, polyester, and nylon textiles. For this purpose, the coated textiles were characterized with profilometry, contact angles, and electrokinetic analyzer measurements. The ZnO NPs on the textiles were analyzed by scanning electron microscopy and inductively coupled plasma mass spectrometry. The antibacterial tests were conducted with S. aureus and biocompatibility with immortalized human keratinocyte cells. The results demonstrated successful PAH/ZnO coating formation on the textiles, demonstrating weak hydrophobic properties. Furthermore, PAH multilayers caused complete ZnO NP immobilization on the coated textiles. All coated textiles showed strong growth inhibition (2–3-log reduction) in planktonic and adhered S. aureus cells. The bacterial viability was reduced by more than 99%. Cotton, due to its better ZnO NP adherence, demonstrated a slightly higher antibacterial performance than polyester and nylon. The coating procedure enables the binding of ZnO NPs in an amount (<30 µg cm⁻²) that, after complete dissolution, is significantly below the concentration causing cytotoxicity (10 µg mL⁻¹). Full article

Protein amyloids have attracted attention for their application as functional amyloid materials because of their strong properties, such as high resistance to chemical or biological degradation, despite their medical issues. Amyloids can be used for various applications by modifying the amyloid surface with functional materials, such as proteins and polymers. In this study, we investigated the effect of polyallylamine (PAA), a functional cationic polymer as a candidate for amyloid modification, on the amyloids formed from amyloid β (Aβ) peptide. It was demonstrated for the first time that PAA can bind to Aβ amyloids through fluorescence observations and the quenched emission from the tyrosine at site 10 near the fibrillogenic core. These results suggest that PAA could be used to develop new functional amyloids. However, notably, coating Aβ amyloid with PAA could affect conventional amyloid detection assays such as thioflavin T assay and detection using antibodies. Thus, our results also indicate that consideration would be necessary for the analysis of functional amyloids coated with various polymers. Full article