Search Results (38)

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

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

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

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

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

Polyelectrolyte multilayers (PEMs) deposited on porous composite polylactic acid/poly(ε-caprolactone) (PDLA/PEC) substrates were studied. The substrates were previously charged in a corona discharge. Time dependences of the normalized surface potential for positively and negatively charged electrets were investigated. The morphology of the obtained porous substrates was examined by means of scanning electron microscopy (SEM). The chitosan and the casein polyelectrolytes were deposited on the substrates using the layer-by-layer (LbL) technique. The drug loading efficiency and the release kinetics were determined spectrophotometrically. Full article

Bacterial infections are a common mode of failure for medical implants. This study aims to develop antibacterial polyelectrolyte multilayer (PEM) coatings that contain a plant-derived condensed tannin polymer (Tanfloc, TAN) with inherent antimicrobial activity. Tanfloc is amphoteric, and herein we show that it can be used as either a polyanion or a polycation in PEMs, thereby expanding the possibility of its use in PEM coatings. PEMs are ordinarily formed using a polycation and a polyanion, in which the functional (ionic) groups of the two polymers are complexed to each other. However, using the amphoteric polymer Tanfloc with weakly basic amine and weakly acidic catechol and pyrogallol groups enables PEM formation using only one or the other of its functional groups, leaving the other functional group available to impart antibacterial activity. This work demonstrates Tanfloc-containing PEMs using multiple counter-polyelectrolytes including three polyanionic glycosaminoglycans of varying charge density, and the polycations N,N,N-trimethyl chitosan and polyethyleneimine. The layer-by-layer (LbL) assembly of PEMs was monitored using in situ Fourier-transform surface plasmon resonance (FT-SPR), confirming a stable LbL assembly. X-ray photoelectron spectroscopy (XPS) was used to evaluate surface chemistry, and atomic force microscopy (AFM) was used to determine the surface roughness. The LDH release levels from cells cultured on the Tanfloc-containing PEMs were not statistically different from those on the negative control (p > 0.05), confirming their non-cytotoxicity, while exhibiting remarkable antiadhesive and bactericidal properties against Pseudomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus), respectively. The antibacterial effects were attributed to electrostatic interactions and Tanfloc’s polyphenolic nature. This work underscores the potential of Tanfloc as a versatile biomaterial for combating infections on surfaces. Full article

The increasing demand for nanofiltration processes in drinking water treatment, industrial separation and wastewater treatment processes has highlighted several shortcomings of current state-of-the-art thin film composite (TFC NF) membranes, including limitations in chemical resistance, fouling resistance and selectivity. Polyelectrolyte multilayer (PEM) membranes provide a viable, industrially applicable alternative, providing significant improvements in these limitations. Laboratory experiments using artificial feedwaters have demonstrated selectivity an order of magnitude higher than polyamide NF, significantly higher fouling resistance and excellent chemical resistance (e.g., 200,000 ppmh chlorine resistance and stability over the 0–14 pH range). This review provides a brief overview of the various parameters that can be modified during the layer-by-layer procedure to determine and fine-tune the properties of the resulting NF membrane. The different parameters that can be adjusted during the layer-by-layer process are presented, which are used to optimize the properties of the resulting nanofiltration membrane. Substantial progress in PEM membrane development is presented, particularly selectivity improvements, of which the most promising route seems to be asymmetric PEM NF membranes, offering a breakthrough in active layer thickness and organic/salt selectivity: an average of 98% micropollutant rejection coupled with a NaCl rejection below 15%. Advantages for wastewater treatment are highlighted, including high selectivity, fouling resistance, chemical stability and a wide range of cleaning methods. Additionally, disadvantages of the current PEM NF membranes are also outlined; while these may impede their use in some industrial wastewater applications, they are largely not restrictive. The effect of realistic feeds (wastewaters and challenging surface waters) on PEM NF membrane performance is also presented: pilot studies conducted for up to 12 months show stable rejection values and no significant irreversible fouling. We close our review by identifying research areas where further studies are needed to facilitate the adoption of this notable technology. Full article

Membrane-based beverage dealcoholization is a successful process for producing low- and non-alcoholic beer and represents a fast-growing industry. Polyamide NF and RO membranes are commonly applied for this process. Polyelectrolyte multilayer (PEM) NF membranes are emerging as industrially relevant species, and their unique properties (usually hollow fiber geometry, high and tunable selectivity, low fouling) underlines the importance of testing them in the food industry as well. To test PEM NF membranes for beer dealcoholization at a small pilot scale, we dealcoholized filtered and unfiltered lager beer with the tightest available commercial polyelectrolyte multilayer NF membrane (NX Filtration dNF40), which has a MWCO = 400 Da, which is quite high for these purposes. Dealcoholization is possible with a reasonable flux (10 L/m²h) at low pressures (5–8.6 bar) with a real extract loss of 15–18% and an alcohol passage of ~100%. Inorganic salt passage is high (which is typical for PEM NF membranes), which greatly affected beer flavor. During the dealcoholization process, the membrane underwent changes which substantially increased its salt rejection values (MgSO₄ passage decreased fourfold) while permeance loss was minimal (less than 10%). According to our sensory evaluation, the process yielded an acceptable tasting beer which could be greatly enhanced by the addition of the lost salts and glycerol. Full article

Polyelectrolyte multilayers (PEM) loaded with bioactive molecules such as proteins serve as excellent mimics of an extracellular matrix and may find applications in fields such as biomedicine and cell biology. A question which is crucial to the successful employment of PEMs is whether conformation and bioactivity of the loaded proteins is preserved. In this work, the polarized attenuated total reflection Fourier transform infrared (ATR-FTIR) technique is applied to investigate the conformation of the protein lysozyme (Lys) loaded into the poly(L-lysine)/hyaluronic acid (PLL/HA) multilayers. Spectra are taken from the protein in the PEMs coated onto an ATR crystal during protein adsorption and desorption. For comparison, a similar investigation is performed for the case of Lys in contact with the uncoated crystal. The study highlights the presence of both “tightly” and “poorly bound” Lys fractions in the PEM. These fractions differ in their conformation and release behavior from the PEM upon washing. Comparison of spectra recorded with different polarizations suggests preferential orientation of alpha helical structures, beta sheets and turns in the “tightly bound” Lys. In contrast, the “poorly bound” fraction shows isotropic orientation and its conformation is well preserved. Full article

The bilayer’s formations of amphiphilic molecules or polyions of different ionogenity comprise the basic building units of most organic biological and non-biological systems. A theory has evolved to explain their behaviour during the creation of those organized structures, such as anisotropic liquid crystal (LC) in lyotropic (especially hydrotropic) systems and polyelectrolyte multilayer (PEM) assemblies. Particular attention has been paid to the temperature and the important role of water in the formation and behaviour of the bilayers. A novel insight into the formation of hydrotropic liquid LC systems and their thermotropic behaviour is presented. In this context, the systems PEM assemblies are also discussed. Essentially, a structuralised form of water fills out continuous and discontinuous, i.e., confined, nano-spaces among hydrophilic interfaces of bilayers, controlling their supramolecular structure through a system of attractive and repulsive hydration forces. The character of those sophisticated bonding hydration systems is predestined by the composition and type of these hydrophilic interface groups. The miscellaneous complexity of the bilayer’s aqueous systems suggests the need to study these examples in greater detail. Therefore, the bilayer’s processes connected with disruption as far as destruction of bilayers are mentioned, i.e., the processes with the highest potential to combat bacteria, fungi, and viruses, such as in a situation where a person exhales a breath of micro-droplets containing virus nanoparticles (e.g., the COVID-19 virus). Full article

Polyelectrolyte multilayers (PEM) are versatile tools used to investigate fundamental interactions between material-related parameters and the resulting performance in stem cell differentiation, respectively, in bone tissue engineering. In the present study, we investigate the suitability of PEMs with a varying collagen content for use as drug carriers for the human bone morphogenetic protein 2 (rhBMP-2). We use three different PEM systems consisting either of the positively charged poly-L-lysine or the glycoprotein collagen type I and the negatively charged glycosaminoglycan heparin. For a specific modification of the loading capacity and the release kinetics, the PEMs were stepwise cross-linked before loading with cytokine. We demonstrate the possibility of immobilizing significant amounts of rhBMP-2 in all multilayer systems and to specifically tune its release via cross-linking. Furthermore, we prove that the drug release of rhBMP-2 plays only a minor role in the differentiation of osteoprogenitor cells. We find a significantly higher influence of the immobilized rhBMP-2 within the collagen-rich coatings that obviously represent an excellent mimicry of the native extracellular matrix. The cytokine immobilized in its bioactive form was able to achieve an increase in orders of magnitude both in the early stages of differentiation and in late calcification compared to the unloaded layers. Full article

Polyelectrolyte multilayers (PEMs) based on polyelectrolyte complex (PEC) structures are recognized as interesting materials for manufacturing functionalized coatings or drug delivery platforms. Difficulties in homogeneous PEC system development generated the idea of chitosan (CS)/low-methoxy amidated pectin (LM PC) multilayer film optimization with regard to the selected variables: the polymer ratio, PC type, and order of polymer mixing. Films were formulated by solvent casting method and then tested to characterize CS/LM PC PECs, using thermal analysis, Fourier transform infrared spectroscopy (FTIR), turbidity, and zeta potential measurements. The internal structure of the films was visualized by using scanning electron microscopy. Analysis of the mechanical and swelling properties enabled us to select the most promising formulations with high uniformity and mechanical strength. Films with confirmed multilayer architecture were indicated as a promising material for the multifunctional systems development for buccal drug delivery. They were also characterized by improved thermal stability as compared to the single polymers and their physical mixtures, most probably as a result of the CS–LM PC interactions. This also might indicate the potential protective effect on the active substances being incorporated in the PEC-based films. Full article

The aim of the present study was to develop a collagen/heparin-based multilayer coating on titanium surfaces for retarded release of recombinant human bone morphogenic protein 2 (rhBMP2) to enhance the osteogenic activity of implant surfaces. Polyelectrolyte multilayer (PEM) coatings were constructed on sandblasted/acid-etched surfaces of titanium discs using heparin and collagen. PEM films of ten double layers were produced and overlayed with 200 µL of a rhBMP2 solution containing 15 µg rhBMP2. Subsequently, cross-linking of heparin molecules was performed using EDC/NHS chemistry to immobilize the incorporated rhBMP2. Release characteristics for 3 weeks, induction of Alkaline Phosphatase (ALP) in C2C12 cells and proliferation of human mesenchymal stem cells (hMSCs) were evaluated to analyze the osteogenic capacity of the surface. The coating incorporated 10.5 µg rhBMP2 on average per disc and did not change the surface morphology. The release profile showed a delivery of 14.5% of the incorporated growth factor during the first 24 h with a decline towards the end of the observation period with a total release of 31.3%. Cross-linking reduced the release with an almost complete suppression at 100% cross-linking. Alkaline Phosphatase was significantly increased on day 1 and day 21, indicating that the growth factor bound in the coating remains active and available after 3 weeks. Proliferation of hMSCs was significantly enhanced by the non-cross-linked PEM coating. Nanocoating using collagen/heparin-based PEMs can incorporate clinically relevant amounts of rhBMP2 on titanium surfaces with a retarded release and a sustained enhancement of osteogenic activity without changing the surface morphology. Full article