Search Results (103)

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

Composite polyethersulfone (PES) membranes containing N-aminoethyl piperazine propane sulfonate (AEPPS)-modified graphene oxide (GO) were integrated with either of the two pretreatment processes (activated carbon (AC) adsorption or polyelectrolyte coagulation) to assess their effectiveness in mitigating membrane fouling during the treatment of abattoir wastewater. The AEPPS@GO-modified membranes, as compared to the pristine PES membranes, showed improved hydrophilicity, with water uptake increasing from 72 to 118%, surface porosity increasing from 2.34 to 27%, and pure water flux (PWF) increasing from 235 to 673 L.m⁻²h⁻¹. The modified membranes presented improved antifouling properties, with the flux recovery ratio (FRR) increasing from 59.5 to 93.3%. This study compared the effectiveness of the two pretreatment processes, AC, coagulation, and the integrated system (coagulation/AC-UF membrane), in the removal of natural organic matter (NOM) and improvement of abattoir wastewater’s pH, electrical conductivity, TDS, and turbidity. The integrated systems produced improved water quality in terms of pH, EC, TDS, turbidity, and organic content. The fluorescence excitation–emission matrix (FEEM) analysis exhibited almost no fluorescence peak post-treatment following organic loading removal. The quality of the water met the South African non-potable water reuse standards. The sole membrane treatment systems exhibited good fouling resistance without the pretreatment systems; however, integrating these systems can offer extended longer filtration periods, thereby assisting in cost aspects of the abattoir wastewater treatment system. Full article

Weak polyelectrolyte chains are versatile polymeric materials due to the large number of functional groups that can be used in different environmental applications. Herein, one weak polycation (polyethyleneimine, PEI) and two polyanions (poly(acrylic acid), PAA, and poly(sodium methacrylate), PMAA) were directly deposited through precipitation of an inter-polyelectrolyte coacervate onto the silica surface (IS), followed by glutaraldehyde (GA) crosslinking and extraction of polyanions chains. Four core–shell composites based on silica were synthesized and tested for adsorption of lead (Pb²⁺) and nickel (Ni²⁺) as model pollutants in batch sorption experiments on the laboratory scale. The sorbed/desorbed amounts depended on the crosslinking degree of the composite shell, as well as on the type of anionic polyelectrolyte. After multiple loading/release cycles of the heavy metal ions, the maximum sorption capacities were situated between 5–10 mg Pb²⁺/g composite and 1–6 mg Ni²⁺/g composite. The strong crosslinked composites (r = 1.0) exhibited higher amounts of heavy metal ions (Me²⁺) sorbed than the less crosslinked ones, with less PEI on the surface but with more flexible chains being more efficient than more PEI with less flexible chains. Core–shell composites based on silica and weak polyelectrolytes could act as sorbent materials, which may be used in water or wastewater treatment. Full article

Biosorption, a non-expensive and easy method for removing potentially toxic metal ions from water, has been the subject of extensive research. In this context, this study introduces a novel approach using sodium alginate and chitosan, versatile biopolymers that have shown excellent results as biosorbents. The challenge of maintaining high efficiencies and reuse is addressed by developing alginate/chitosan-based films. These films, prepared using solvent casting and crosslinking methods, form a hydrogel network. The alginate/chitosan-based films, obtained using the eco-friendly polyelectrolyte complex method, were characterized by FTIR, SEM, TGA, and DSC. The study of their swelling pH response, adsorption, and desorption behavior revealed promising results. The adsorption of Pb was significantly enhanced by the presence of both biopolymers (98%) in a shorter time (15 min) at pH = 6.5. The adsorption of both ions followed a pseudo-second-order kinetic and the Langmuir isotherm model. The desorption efficiencies for Cd and Pb were 98.8% and 77.6% after five adsorption/desorption cycles, respectively. In conclusion, the alginate/chitosan-based films present a highly effective and novel approach for removing Cd and Pb from water, with a promising potential for reuse, demonstrating their strong potential in potentially toxic metal removal. 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

Amidoxime-functionalized hydrogels are one of most promising adsorbents for high-efficiency uranium (U) extraction from seawater, but bioadhesion on their surface seriously decreases their adsorption efficiency and largely shortens their service life. Herein, a semi-interpenetrating zwitterion–poly(amidoxime) (ZW-PAO) hydrogel was explored through introducing a PAO polymer into a poly [3-(dimethyl 4-vinylbenzyl amino) propyl sulfonate] (PDVBAP) polyzwitterionic (PZW) network via ultraviolet (UV) polymerization. Owing to the anti-polyelectrolyte effect of the PZW network, this ZW-PAO hydrogel can provide excellent super-hydrophilicity in seawater for high-efficiency U-adsorption from seawater. Furthermore, the ZW-PAO hydrogel had outstanding anti-biofouling performance for both highly enhanced U-adsorption and a relatively long working life in natural seawater. As a result, during only 25 days in seawater (without filtering bacteria), the U-uptake amount of this ZW-PAO hydrogel can reach 9.38 mg/g and its average rate can reach 0.375 mg/(g∙day), which is excellent among reported adsorbents. This work has explored a promising hydrogel for high-efficiency U-recovery from natural seawater and will inspire new strategy for U-adsorbing materials. 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

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

This work explores the effects of rigid (0.1, 0.25, and 0.5 wt. %) and semi-flexible (0.5, 1.0, and 2.5 wt. %) all-aromatic polyelectrolyte reinforcements as rheological and morphological modifiers for preparing phosphate geopolymer glass–ceramic composites. Polymer-modified aluminosilicate–phosphate geopolymer resins were prepared by high-shear mixing of a metakaolin powder with 9M phosphoric acid and two all-aromatic, sulfonated polyamides. Polymer loadings between 0.5–2.5 wt. % exhibited gel-like behavior and an increase in the modulus of the geopolymer resin as a function of polymer concentration. The incorporation of a 0.5 wt. % rigid polymer resulted in a three-fold increase in viscosity relative to the control phosphate geopolymer resin. Hardening, dehydration, and crystallization of the geopolymer resins to glass-ceramics was achieved through mold casting, curing at 80 °C for 24 h, and a final heat treatment up to 260 °C. Scanning electron microscopy revealed a decrease in microstructure porosity in the range of 0.78 μm to 0.31 μm for geopolymer plaques containing loadings of 0.5 wt. % rigid polymer. Nano-porosity values of the composites were measured between 10–40 nm using nitrogen adsorption (Brunauer–Emmett–Teller method) and transmission electron microscopy. Nanoindentation studies revealed geopolymer composites with Young’s modulus values of 15–24 GPa and hardness values of 1–2 GPa, suggesting an increase in modulus and hardness with polymer incorporation. Additional structural and chemical analyses were performed via thermal gravimetric analysis, Fourier transform infrared radiation, X-ray diffraction, and energy dispersive spectroscopy. This work provides a fundamental understanding of the processing, microstructure, and mechanical behavior of water-soluble, high-performance polyelectrolyte-reinforced geopolymer composites. Full article

Biofouling is a great challenge for engineering material in medical-, marine-, and pharmaceutical-related applications. In this study, a novel trimethylamine N-oxide (TMAO)–analog monomer, 3-(2-methylacrylamido)-N,N-dimethylpropylamine N-oxide (MADMPAO), was synthesized and applied for the grafting of poly(MADMPAO) (pMPAO) brushes on quartz crystal microbalance (QCM) chips by the combination of bio-inspired poly-dopamine (pDA) and surface-initiated atom transfer radical polymerization technology. The result of ion adsorption exhibited that a sequential pDA and pMPAO arrangement from the chip surface had different characteristics from a simple pDA layer. Ion adsorption on pMPAO-grafted chips was greatly inhibited at low salt concentrations of 1 and 10 mmol/L due to strong surface hydration in the presence of charged N⁺ and O⁻ of zwitterionic pMPAO brushes on the outer layer on the chip surface, well known as the “anti-polyelectrolyte” effect. During BSA adsorption, pMPAO grafting also led to a marked decrease in frequency shift, indicating great inhibition of protein adsorption. It was attributed to weaker BSA-pMPAO interaction. In this study, the Au@pDA-4-pMPAO chip with the highest coating concentration of DA kept stable dissipation in BSA adsorption, signifying that the chip had a good antifouling property. The research provided a novel monomer for zwitterionic polymer and demonstrated the potential of pMPAO brushes in the development and modification of antifouling materials. 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

The adsorption kinetics of human serum albumin (HSA) on bare and poly-L-arginine (PARG)-modified silica substrates were investigated using reflectometry and atomic force microscopy (AFM). Measurements were carried out at various pHs, flow rates and albumin concentrations in the 10 and 150 mM NaCl solutions. The mass transfer rate constants and the maximum protein coverages were determined for the bare silica at pH 4.0 and theoretically interpreted in terms of the hybrid random sequential adsorption model. These results were used as reference data for the analysis of adsorption kinetics at larger pHs. It was shown that the adsorption on bare silica rapidly decreased with pH and became negligible at pH 7.4. The albumin adsorption on PARG-functionalized silica showed an opposite trend, i.e., it was negligible at pH 4 and attained maximum values at pH 7.4 and 150 mM NaCl, the conditions corresponding to the blood serum environment. These results were interpreted as the evidence of a significant role of electrostatic interactions in the albumin adsorption on the bare and PARG-modified silica. It was also argued that our results can serve as useful reference data enabling a proper interpretation of protein adsorption on substrates functionalized by polyelectrolytes. Full article

Silk fibroin (SF) is a protein with many outstanding properties (superior biocompatibility, mechanical strength, etc.) and is often used in many advanced applications (epidermal sensors, tissue engineering, etc.). The properties of SF-based biomaterials may additionally be tuned by SF interactions with other (bio)polymers. Being a weak amphoteric polyelectrolyte, SF may form polyelectrolyte complexes (PECs) with other polyelectrolytes of opposite charge, such as poly(acrylic acid) (PAA). PAA is a widely used, biocompatible, synthetic polyanion. Here, we investigate PEC formation between SF and PAA of two different molecular weights (MWs), low and high, using various techniques (turbidimetry, zeta potential measurements, capillary viscometry, and tensiometry). The colloidal properties of SF isolated from Bombyx mori and of PAAs (MW, overlap concentration, the influence of pH on zeta potential, adsorption at air/water interface) were determined to identify conditions for the SF-PAA electrostatic interaction. It was shown that SF-PAA PEC formation takes place at different SF:PAA ratios, at pH 3, for both high and low MW PAA. SF-PAA PEC’s properties (phase separation, charge, and surface activity) are influenced by the SF:PAA mass ratio and/or the MW of PAA. The findings on the interactions contribute to the future development of SP-PAA PEC-based films and bioadhesives with tailored properties. Full article

Allapinin has antiarrhythmic activity and can be used to prevent and treat various supraventricular and ventricular arrhythmias. Nevertheless, it is highly toxic and has a number of side effects associated with non-specific accumulation in various tissues. The complex of this substance with the monoammonium salt of glycyrrhizic acid (Al:MASGA) has less toxicity and improved antiarrhythmic activity. However, the encapsulation of Al:MASGA in polyelectrolyte microcapsules (PMC) for prolonged release will reduce the residual adverse effects of this drug. In this work, the possibility of encapsulating the allapinin–MASGA complex in polyelectrolyte microcapsules based on polyallylamine and polystyrene sulfonate was investigated. The encapsulation methods of the allapinin–MASGA in polyelectrolyte microcapsules by adsorption and coprecipitation were compared. It was found that the coprecipitation method did not result in the encapsulation of Al:MASGA. The sorption method facilitated the encapsulation of up to 80% of the original substance content in solution in PMC. The release of the encapsulated substance was further investigated, and it was shown that the release of the encapsulated Al:MASGA was independent of the substance content in the capsules, but at pH 5, a two-fold decrease in the rate of drug release was observed. 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