Search Results (149)

The formation of mixed adsorption layers of amyloid fibrils of a plant protein, oat globulin (OG), and a strong polyelectrolyte, sodium polystyrene sulfonate (PSS), at the liquid–gas interface was studied by measurements of the kinetic dependencies of surface tension, dynamic surface elasticity, and ellipsometric angle. The micromorphology of the layers was determined by atomic force microscopy. A strong increase in the surface elasticity was discovered when both components had similar concentrations and formed a network of threadlike aggregates at the interface, thereby explaining the high foam stability in this concentration range. The sequential adsorption of PSS and OG resulted in the formation of thick mixed multilayers and the surface elasticity increased with the number of duplex layers. Full article

A novel glucose biosensor is developed based on a tilted fiber Bragg grating (TFBG) functionalized with a pH-responsive polyelectrolyte multilayer membrane, onto which glucose oxidase (GOD) is immobilized. The sensing film is constructed via layer-by-layer self-assembly of poly(ethylenimine) (PEI) and poly(acrylic acid) (PAA), which undergoes reversible swelling and refractive index (RI) changes in response to local pH variations. These changes are transduced into measurable shifts in the resonance wavelengths of TFBG cladding modes. The catalytic action of GOD oxidizes glucose to gluconic acid, thereby modulating the interfacial pH and actuating the polyelectrolyte membrane. With an optimized (PEI/PAA)₄(PEI/GOD)₁ structure, the biosensor achieves highly sensitive glucose detection, featuring a wide measurement range (10⁻⁸ to 10⁻² M), a low detection limit of 27.7 nM, and a fast response time of ~60 s. It also demonstrates excellent specificity and robust performance in complex biological matrices such as rabbit serum and artificial urine, with recovery rates of 93–102%, highlighting its strong potential for point-of-care testing applications. This platform offers significant advantages in stability, temperature insensitivity, and miniaturization, making it well-suited for clinical glucose monitoring and disease management. Full article

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

Nanofiltration (NF) technology has extensive application in the treatment of wastewater generated in the dyeing industry. However, NF membranes often encounter fouling issues during the operation process. In this work, the superhydrophilic and self-cleaning multilayer nanofiltration membrane was prepared by self-assembling polyelectrolyte incorporating the anatase PSS-TiO₂ nanoparticles. The negatively charged PSS-TiO₂ nanoparticles were beneficial to the formation of the nanohybrid selective layers via electrostatic interforce. The prepared (PEI/PSS-TiO₂)_4.0 hybrid membrane showed favorable photoinduced superhydrophilicity. The water contact angle of the membrane decreased with the UV irradiation from 35.7° to 1.6°. The negatively charged (PEI/PSS-TiO₂)_4.0 membrane exhibited a 100% rejection rate to XO and EbT, with a permeance flux of 5.2 and 6.4 L/(m²·h·bar), respectively. After UV irradiation for 60 min, the permeance flux could be further increased to 13.4 and 14.0 L/(m²·h·bar), and the rejection remained at 97.8% and 96.7%. Owing to the low content of TiO₂ NPs photocatalytic effect under UV irradiation, the fabricated hybrid membrane exhibited a compromised permeance recovery of about 80.6%. 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

Polydopamine (Pdop) particles possess unique properties but suffer from inherent instability in aqueous environments due to the gradual release of Pdop fragments. This study demonstrated the successful enhancement of the stability and reduction in fragmentation in Pdop particles through surface engineering strategies. Specifically, we investigated the effects of polyelectrolyte multilayer (PEM) coating and polyelectrolyte (PE) brush grafting. Our results showed that PE brush grafting, particularly with long-chain polyethyleneimine (PEI), was more effective in suppressing Pdop fragment release compared to PEM coating. The L-PEI grafted Pdop particles (2.28 chains/nm²) exhibited remarkable stability across a wide pH range (3–9), with inhibition rates exceeding 90% in most cases, reaching 93% at pH 5. Furthermore, a direct correlation between PEI grafting density (0.64 to 2.28 chains/nm²) and inhibition rate was observed, with higher densities yielding greater stability. These findings offer a promising approach for stabilizing Pdop particles for diverse applications. Full article

This study examines the effects of natural organic matter (NOM) and dissolved solids on fluoride (F⁻) retention in polyelectrolyte multilayer-based hollow-fiber nanofiltration membranes (dNF40). Lab-scale filtration experiments were conducted under varying operating conditions (initial salt concentration, NOM concentration, permeate flux, crossflow velocity, and recovery rate). dNF40 membranes exhibited F⁻ retention above 70% ± 1.2 in the absence of NOM and competing ions. However, when filtering synthetic model water (SMW) designed to simulate groundwater contaminated with high total dissolved solids (TDSs) and NOM, F⁻ retention decreased to approximately 60% ± 0.7, which was generally attributed to ion competition. Furthermore, despite limited declines in normalized permeability, the addition of NOM to SMW notably deceased F⁻ retention in the steady state to~20% due to fouling effects. The facilitated transport of the divalent cations Ca²⁺ and Mg²⁺ could be observed, as they accumulated in the organic fouling layer. While SO₄²⁻ retention remained relatively stable, the retention of monovalent anions (NO₃⁻, Cl⁻, and F⁻) decreased substantially due to drag effects. Na⁺ retention improved slightly to maintain electroneutrality. Feed salinity was shown to significantly affect separation efficiency, with PEC layers undergoing swelling and certain structural changes as the ionic strength increased. During batch filtration experiments at varying recovery rates, the retention of monovalent anions further decreased, with F⁻ retention reducing to just ~10% at a 90% recovery rate. This study provides valuable insights into better understanding and optimizing the performance of PEC-based NF membranes across diverse water treatment scenarios. Full article

Polyelectrolyte multilayers (PEMs) deposited on non-porous and porous blend substrates were studied. Films, prepared from two biodegradable polymers poly (D-lactic acid) (PDLA) and poly(ε-caprolactone) (PCL) and their blends were used as substrates in the present paper. All films were initially charged in a corona discharge (positive or negative corona). After charging, the initial surface potential of the samples V₀ was measured and the normalized surface potential was calculated. The dependencies on time of the normalized surface potential for electrets, possessing either positive or negative charges, were studied. It was found that the steady-state values of the normalized surface potential for the porous substrates were higher than those of the non-porous ones, independently of material type and corona polarity. It was also shown that the values of the normalized surface potential for the PCL electrets were the highest and decreased when the content of PDLA increased. Scanning electron microscopy (SEM) was utilized for the determination of the substrates’ surface morphology. With the largest pore size, PCL substrates allowed for a greater capture of charges on their surface and facilitated the retention of said charges for prolonged periods of time. Differential scanning calorimetry (DSC) measurements were performed to determine the degree of crystallinity, which was very high for PCL substrates, when compared to the other investigated substrates. The wettability of the investigated substrates was measured using the static water contact angle method. The obtained results demonstrated that the created blends were more hydrophilic than the pure films. The two chosen polyelectrolytes were layered onto the surface of the substrates with the use of the layer-by-layer (LbL) technique and benzydamine hydrochloride was loaded in the multilayers as a model drug. Its loading efficiency and release profile were carried out spectrophotometrically. It was determined that for non-porous substrates, independently of the corona polarity, the best fitting model was Korsmeyer-Peppas, while for the porous substrates the best fitting model was Weibull. Full article

The aim of the present study was to test the sequential and simultaneous release of rhBMP2 and rhVEGF165 from poly-l-lysine-heparin (PLL-Hep) poly-electrolyte multilayer (PEM) coating on titanium surfaces for their ability to enhance peri-implant bone formation and CD31 expression around disc-shaped titanium implants (5 × 7 mm) in mini-pig mandibles. Bare titanium surfaces loaded with respective growth factor combinations served as controls. Ten different surface conditions were tested exhibiting early VEGF release, early BMP release, simultaneous VEGF and BMP release, and sole VEGF/BMP release, respectively. The implants were inserted press-fit into 5 mm trephine cavities at the lower border of the mandibles of mini-pigs and left to heal for 4 and 13 weeks. After 4 weeks, there was no significant difference in peri-implant bone formation, bone–implant contact nor CD31 expression between the different surface conditions. After 13 weeks, bone formation was significantly higher in the zone of 100 μm next to implant surfaces releasing either BMP alone or with an early release of BMP2. Expression of CD31 has significantly decreased from 4 to 13 weeks with significantly higher values in the group of implants with early release of BMP2. The results indicate that the range of released growth factors is limited to a distance of approximately 100 μm and that the sequence of early release of BMP2 followed by VEGF165 promotes peri-implant bone formation and peri-implant angiogenesis, which is in contrast to the current understanding of the temporal patterns of growth factor release for enhancement of bone formation. Full article

To reduce the risk of side effects and enhance therapeutic efficiency, drug delivery systems that offer precise control over active ingredient release while minimizing burst effects are considered advantageous. In this study, a novel approach for the controlled release of lamivudine (LV) was explored through the fabrication of polyelectrolyte-coated microparticles. LV was covalently attached to poly(ε-caprolactone) via ring-opening polymerization, resulting in a macromolecular prodrug (LV-PCL) with a hydrolytic release mechanism. The LV-PCL particles were subsequently coated using the layer-by-layer (LbL) technique, with polyelectrolyte multilayers assembled to potentially modify the carrier’s properties. The LbL assembly process was comprehensively analyzed, including assessments of shell thickness, changes in ζ-potential, and thermodynamic properties, to provide insights into the multilayer structure and interactions. The sustained LV release over 7 weeks was observed, following zero-order kinetics (R² > 0.99), indicating a controlled and predictable release mechanism. Carriers coated with polyethylene imine/heparin and chitosan/heparin tetralayers exhibited a distinct increase in the release rate after 6 weeks and 10 weeks, respectively, suggesting that this coating can facilitate the autocatalytic degradation of the polyester microparticles. These findings indicate the potential of this system for long-term, localized drug delivery applications, requiring sustained release with minimal burst effects. 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

The formation of beta-lactoglobulin (BLG)/sodium polystyrene sulfonate (PSS) complexes decelerates the change in the surface properties of the mixed solutions with the surface age and increases the steady-state dilational surface elasticity in a narrow PSS concentration range. At the same time, the changes in the surface properties are accelerated in the dispersions of BLG fibrils with and without PSS due to the influence of small peptides coexisting with fibrils. A decrease in the peptide concentration as a result of the dispersion purification leads to slower changes in the surface properties at low PSS concentrations. The increase in the polyelectrolyte concentration results in an increase in the steady-state surface elasticity due to the fibril/PSS complex formation and in very slow changes in the surface properties if the polyelectrolyte exceeds a certain critical value. The latter effect is a consequence of the formation of large aggregates and of an increase in the electrostatic adsorption barrier. The consecutive adsorption of BLG fibrils and PSS leads to the formation of regular multilayers at the liquid–gas interface. The multilayer properties change noticeably with an increase in the number of layers from four to six in agreement with previous results on the multilayers of PSS with an oppositely charged synthetic polyelectrolyte, presumably due to the heterogeneity of the first PSS layer. The dynamic elasticity of the multilayers approaches 250 mN/m, indicating that they can effectively stabilize foams and emulsions. Full article

Three-dimensional printing (3DP) has emerged as a promising method for creating intricate scaffold designs. This study assessed three 3DP scaffold designs fabricated using biodegradable poly(lactic) acid (PLA) through fused deposition modelling (FDM): mesh, two channels (2C), and four channels (4C). To address the limitations of PLA, such as hydrophobic properties and poor cell attachment, a post-fabrication modification technique employing Polyelectrolyte Multilayers (PEMs) coating was implemented. The scaffolds underwent aminolysis followed by coating with SiCHA nanopowders dispersed in hyaluronic acid and collagen type I, and finally crosslinked the outermost coated layers with EDC/NHS solution to complete the hybrid scaffold production. The study employed rotating wall vessels (RWVs) to investigate how simulating microgravity affects cell proliferation and differentiation. Human mesenchymal stem cells (hMSCs) cultured on these scaffolds using proliferation medium (PM) and osteogenic media (OM), subjected to static (TCP) and dynamic (RWVs) conditions for 21 days, revealed superior performance of 4C hybrid scaffolds, particularly in OM. Compared to commercial hydroxyapatite scaffolds, these hybrid scaffolds demonstrated enhanced cell activity and survival. The pre-vascularisation concept on 4C hybrid scaffolds showed the proliferation of both HUVECs and hMSCs throughout the scaffolds, with a positive expression of osteogenic and angiogenic markers at the early stages. Full article

Controlling cell adhesion, viability, and proliferation on solid surfaces is critical for the successful implantation and proper functioning of temporary and permanent medical devices. While, with temporary or removable implants as well as surgical instruments, even slight cellular adhesion leads to an increased risk of secondary infections, bleeding and other complications, good cellular adhesion and viability are essential for the rapid healing and successful integration of permanent implants. This work was motivated by the growing interest in the construction of biocompatible and biodegradable coatings for the biofunctionalization of medical devices. Polysaccharide-based coatings are well known for their biocompatibility, but they are non-cell-adhesive, which hinders their application as implant coatings. In this study, we demonstrate that the incorporation of one or more graphene oxide layers in hyaluronic acid/chitosan multilayers is one avenue to regulate the degree of unspecific adhesion and growth of different cells (human umbilical vein endothelial cells, HUVEC, and mouse embryonic fibroblasts, 3T3). Furthermore, we demonstrate that this approach allows cell adhesion to be regulated across the entire range between completely prevented and highly promoted cell adhesion without introducing systemic cytotoxicity. These findings may contribute to the establishment of a new approach to adapt medical devices to cells and tissues. Full article

Water scarcity and contamination have emerged as critical global challenges, requiring the development of effective and sustainable solutions for the treatment of contaminated water. Recently, functionalized polymer biomaterials have garnered significant interest because of their potential for a wide range of water treatment applications. Accordingly, this paper highlights the design of a new adsorbent material based on a cellulosic nonwoven textile grafted with two extracted biopolymers. The layer-by-layer grafting technique was used for the polyelectrolyte multi-layer (PEM) biosorbent production. Firstly, we extracted a Suaeda fruticosa polysaccharide (SFP) and confirmed its pectin-like polysaccharide structure via SEC, NMR spectroscopy, and chemical composition analyses. Afterward, the grafting was designed via an alternating multi-deposition of layers of SFP polymer and carrageenan crosslinked with 1,2,3,4-butanetetracarboxylic acid (BTCA). FT-IR and SEM were used to characterize the chemical and morphological characteristics of the designed material. Chemical grafting via polyesterification reactions of the PEM biosorbent was confirmed through FT-IR analysis. SEM revealed the total filling of material microspaces with layers of grafted biopolymers and a rougher surface morphology. The assessment of the swelling behavior revealed a significant increase in the hydrophilicity of the produced adsorbent system, a required property for efficient sorption potential. The evaluation of the adsorption capabilities using the methylene blue (MB) as cationic dye was conducted in various experimental settings, changing factors such as the pH, time, temperature, and initial concentration of dye. For the untreated and grafted materials, the greatest adsorbed amounts of MB were 130.6 mg/g and 802.6 mg/g, respectively (pH = 4, T = 22 C, duration = 120 min, and dye concentration = 600 mg/L). The high adsorption performance, compared to other reported materials, was due to the presence of a large number of hydroxyl, sulfonate, and carboxylic functional groups in the biosorbent polymeric system. The adsorption process fitted well with the pseudo-first-order kinetic model and Langmuir/Temkin adsorption isotherms. This newly developed multi-layered biosorbent shows promise as an excellent adsorption resultant and cheap-cost/easy preparation alternative for treating industrial wastewater. Full article