Search Results (41)

Silica-modified electrodes possess physicochemical properties that make them valuable in electrochemical sensing and energy-related applications. Although intrinsically insulating, silica thin films can selectively interact with redox species, producing sieving effects that enhance electrochemical responses. We synthesized Class I hybrid silica matrices incorporating either negatively charged poly(4-styrene sulfonic acid) or positively charged poly(diallyl dimethylammonium chloride). These hybrid films were deposited onto ITO electrodes and evaluated via cyclic voltammetry in aqueous ferrocenium solutions. The polyelectrolyte charge played a key role in the electroassisted incorporation of ferrocene: silica-PSS films promoted accumulation, while silica-PDADMAC films hindered it due to electrostatic repulsion. In situ UV-vis spectroscopy confirmed that only a fraction of the embedded ferrocene was electroactive. Nevertheless, this fraction enabled effective mediated detection of cytochrome c in solution. These findings highlight the crucial role of ionic interactions and hybrid composition in electron transfer to redox proteins, providing valuable insights for the development of advanced bioelectronic sensors. Full article

A modified activated carbon (AC) was developed by modifying with poly(diallyldimethylammonium) chloride (PDADMAC) to enhance its adsorption performance for water treatment applications. Different PDADMAC concentrations were explored and evaluated using methyl red as a model contaminant, with 8 w/v% PDADMAC yielding the best adsorption performance. The kinetics data were well described by the pseudo-first-order equation and homogeneous surface diffusion model. The Freundlich isotherm fit the equilibrium data well, indicating multilayer adsorption and diverse interaction types. The removal efficiency remained similar across a pH range of 5–9 and in the presence of background inorganic (NaCl)/organic compounds (sodium acetate) at different concentrations. Rapid small-scale column tests were performed to simulate continuous flow conditions, and the PDADMAC-modified AC effectively delayed the breakthrough of the contaminant compared to raw AC. Regeneration experiments showed that 0.1 M NaOH with 70% methanol effectively restored the adsorption capacity, retaining 80% of the initial efficiency after five cycles. Quantum chemical analysis revealed that non-covalent interactions, including electrostatic and Van der Waals forces, governed the adsorption mechanism. Overall, the results of this study prove that PDADMAC-AC shows great potential for enhanced organic contaminant removal in water treatment systems. Full article

A novel, eco-friendly and cost-effective adsorbent, poly(diallyldimethylammonium) chloride (PDADMAC)-modified clay was developed to enhance its efficacy in removing Methyl Red (MR) from water. Different concentrations of PDADMAC solutions were evaluated during the synthesis and the effects of different operating conditions were investigated. The kinetic data closely followed the pseudo-first-order model, while equilibrium data were well described by Freundlich isotherm. MR removal efficiency decreased as solution pH or NaCl concentration increased, suggesting that electrostatic interaction plays a key role in the adsorption process. Regeneration studies using NaCl solutions revealed that a 1% NaCl solution effectively restored the adsorbent’s capacity. The findings indicate that PDADMAC clay is a promising and sustainable adsorbent for MR removal. Additionally, a three-layer backpropagation artificial neural network (ANN) was developed to predict the MR removal efficiency based on the initial MR concentration, pH, NaCl concentration, and adsorption time. Among these variables, pH was identified as the most influential factor. This approach provides valuable insight into the outcome prediction of a given adsorption process. 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

Mercury (Hg) is a toxic element which impacts on biological systems and ecosystems. Because the toxicity of Hg species is highly dependent on their concentration levels and chemical forms, the sensitive identification of the chemical forms of Hg—i.e., Hg speciation—is of major significance in providing meaningful information about the sources of Hg exposure. In this study, a microfluidic-based device made of high-clarity poly(methyl methacrylate) (PMMA) was fabricated. Then, titanium dioxide nanoparticles (nano-TiO₂s) were attached to the treated channel’s interior with the aid of poly(diallyldimethylammonium chloride) (PDADMAC). After coupling the nano-TiO₂-coated microfluidic-based photocatalyst-assisted reduction device (the nano-TiO₂-coated microfluidic-based PCARD) with high-performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS), a selective and sensitive, hyphenated system for Hg speciation was established. Validation procedures demonstrated that the method could be satisfactorily applied to the determination of mercury ions (Hg²⁺) and methylmercury ions (CH₃Hg⁺) in both human urine and water samples. Remarkably, the zeta potential measured clearly indicated that the PDADMAC-capped nano-TiO₂s with a predominance of positive charges indeed provided a steady force for firm attachment to the negatively charged device channel. The cause of the durability of the nano-TiO₂-coated microfluidic-based PCARD was clarified thus. Full article

The main purpose of this paper was to reveal the effect of aluminum (Al)-based coagulants on enhanced coagulation for the removal of algae and the synergistic optimization mechanism among different Al species. The formation, breakage, and regrowth processes of algal coagulation flocs formed by a series of monomeric Al-based coagulants (Al₂(SO₄)₃, Al₁₃, and Al₃₀), Al₁₃/Al₃₀ composite coagulant and poly(diallyldimethylammonium chloride)/Al₁₃ (PDADMAC/Al₁₃) composite coagulant were studied. Results indicated that Al₁₃ mainly employed a charge neutralization mechanism, which was conducive to the destabilization of algae and the regeneration of flocs, while Al₃₀ mainly employed a sweep flocculation mechanism, which was conducive to the formation of algae and the strength of flocs. Meanwhile, the charge neutralization was the main mechanism during the algae coagulation process because it could effectively remove the soluble microbial products (SMP) component in the extracellular organic matter (EOM). Therefore, Al₁₃ could achieve a higher coagulation performance than other monomeric Al-based coagulants. The Al₁₃/Al₃₀ composite coagulant could make up for the deficiency of the sweep flocculation mechanism in Al₁₃ and charge neutralization mechanism in Al₃₀, and achieve the best synergistic optimization performance at Al₁₃:Al₃₀-7:3. Additionally, PDADMAC, as a polymer, could further enhance the charge neutralization ability of Al₁₃ at low dosages and the sweep flocculation ability of Al₁₃ at high dosages, respectively. However, an excessive dosage would lead to charge reversal and thus reduce the coagulation effect. Therefore, controlling the dosage was key when using Al-composite coagulants. The findings of our research could offer a certain theoretical foundation for the development of inorganic polymer flocculants. Full article

Swine wastewater (SW) was treated using industrial wastes as raw materials in a pre-treatment process (coagulation or adsorption), followed by a continuous heterogeneous Fenton reaction. Before the treatment conducted as a continuous operation, two different batch optimization strategies were evaluated, in which the effects of H₂O₂ concentration and pH were studied. The results show that using excessive H₂O₂ results in the same behavior, regardless of whether the pH is 3 or 7.5, while at low H₂O₂ concentrations, the acidic pH improves the chemical oxygen demand (COD) removal due to a higher solubility of iron. The partial addition of H₂O₂ after 60 min of the reaction proved to be unbeneficial. Considering other perspectives, a continuous Fenton process using iron filings (IF) as the iron source ([H₂O₂] = 50 mg/L) was applied after the SW pre-treatment, consisting of adsorption with red mud (RM) or coagulation with poly-diallyldimethylammonium chloride (PDADMAC). The RM adsorption presented higher COD removal and lower toxicity than the PDADMAC coagulation, revealing to be a suitable material for this purpose, but for both pre-treatments, the application of a subsequent continuous Fenton process revealed to be essential to achieve the COD discharge limits imposed by the Portuguese law. In addition, high amounts of dissolved iron were present in the samples (55–58 mg/L) after the Fenton process. However, after the overall treatment, the samples showed no harmful characteristics for Lepidium sativum, being classified as “non-toxic”, contrary to the initial wastewater. Full article

Biocidal coatings are of great interest to the healthcare system. In this work, the biocidal activity of coatings based on a complex biocide containing polymer and inorganic active antibacterial components was studied. Silver oxide was distributed in a matrix of a positively charged interpolyelectrolyte complex (IPEC) of polydiallyldimethylammonium chloride (PDADMAC) and sodium polystyrene sulfonate (PSS) using ultrasonic dispersion, forming nanoparticles with an average size of 5–6 nm. The formed nanoparticles in the matrix are not subject to agglomeration and changes in morphology during storage. It was found that the inclusion of silver oxide in a positively charged IPEC allows a more than 4-fold increase in the effectiveness of the complex biocide against E. coli K12 in comparison with the biocidal effect of PDADMAC and IPEC. Polycation, IPEC, and the IPEC/Ag₂O ternary complex form coatings on the glass surface due to electrostatic adsorption. Adhesive and cohesive forces in the resulting coatings were studied with micron-scale coatings using dynamometry. It was found that the stability of the coating is determined primarily by adhesive interactions. At the macro level, it is not possible to reliably identify the role of IPEC formation in adhesion. On the other hand, use of the optical tweezers method makes it possible to analyze macromolecules at the submicron scale and to evaluate the multiple increase in adhesive forces when forming a coating from IPEC compared to coatings from PDADMAC. Thus, the application of ternary IPEC/Ag₂O complexes makes it possible to obtain coatings with increased antibacterial action and improved adhesive characteristics. Full article

Positively charged polyelectrolytes hold significant potential as materials for creating antibacterial coatings. We examined the physicochemical and mechanical properties of the macromolecules in water solutions and in coatings for the series of branched polyethyleneimine (PEI) and linear polydiallyldimethylammonium chloride (PDADMAC) with different molecular weights. The microbiological study was conducted to analyze the biocidal activity of the polycation solutions and coatings towards foodborne bacteria. While the moisture saturation of the polycationic coatings and biocidal activity did not significantly depend on the chemical nature of charged groups or the molecular weight or architecture of macromolecules, the lowering of the molecular weight of polymers resulted in the loss of cohesive forces in the coatings and to a dramatic loss of stability when being washed off with water. The diffusion coefficient (D₀) of macromolecules was identified as a key parameter for the wash-off mechanism. Films formed by molecules with a D₀ below 1 × 10⁻⁷ cm²/s demonstrated a high resistance to wash-off procedures. We demonstrated that PEI and PDADMAC samples with high molecular weights showed high antimicrobial activity towards L. monocytogenes. Our results highlight the importance of macromolecule characteristics in the development of new biocidal coatings based on polycations. Full article

Poly-diallyldimethylammonium (PDADMAC) chloride is a flocculant agent extensively used in water clarification treatments. Commercial polyelectrolyte formulations often contain residual monomer (DADMAC), reaction by-products and other reactants as contaminants that could potentially affect human health. In the present study, we optimized an analytical method based on reversed-phase ion-pair chromatography coupled with mass spectrometry for quantifying ultra-trace levels of DADMAC, without preliminary treatments, in drinking water distributed by the Palermo aqueduct. The method was validated in terms of accuracy (recovery between 80 to 120%), precision (RSD < 10%), linearity range (from 0.5 to 15 µg/L), limit of quantification and limit of detection (LOQ 0.42 µg/L and LOD 0.12 µg/L). DADMAC was detected in all analysed water samples and the concentration ranged from 1.2 to 3.8 µg/L whit a mean value of 1.7 µg/L. To the best of our knowledge, this paper represents the first study concerning DADMAC concentration in water samples collected in Italy and, in this context, this paper can be considered very interesting when comparing future data on DADMAC monitoring in water. Moreover, this is one of a few cases where DADMAC was found in drinking water. Full article

Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and the degree of polymerisation in this block. Depending on the architecture of the hydrophobic part, they had a more or less pronounced tendency to form copolymer micelles in an aqueous solution. They were employed for the preparation of IPECs by mixing the copolymer aggregates with the polycations polydiallyldimethylammonium chloride (PDADMAC) or q-chit. The IPEC structure as a function of the composition was investigated by Static Light and Small Angle Neutron Scattering. For weakly-associated block copolymers (short alkyl chain), complexation with polycation led to the formation of globular complexes, while already existing micelles (long alkyl chain) grew further in mass. In general, aggregates became larger upon the addition of further polycation, but this growth was much more pronounced for PDADMAC compared to q-chit, thereby leading to the formation of clusters of aggregates. Accordingly, the structure of such IPECs with a hydrophobic block depended largely on the type of complexing polyelectrolyte, which allowed for controlling the structural organisation via the molecular architecture of the two oppositely charged polyelectrolytes. Full article

Aqueous formulations based on anionic butadiene-styrene microspheres (BSMs) and cationic poly(diallyldimethylammonium chloride) (PDADMAC) with the weight PDADMAC fraction from 0 to 1 were studied as the stabilizers of loose sandy soils. In general, these systems were shown to be represented as the mixtures of microspheres saturated with PDADMAC and unbound polycation. Mechanical testing of BSMs–PDADMAC films evidenced that with increasing weight PDADMAC fraction, a 20-fold growth in elastic modulus, 2-fold growth in strength and 2-fold decrease in ultimate strain of the material were observed. Treatment of the sand with the above formulations resulted in formation of a protective porous polymer-sand surface crust with the strength from 0.8 to 45.0 MPa. “Elasticity–rigidity” balance and water resistance of the crusts were controlled by weight fraction of polycation in the mixed formulation. Stable water-resistant polymer-sand crusts were shown to be prepared using formulations with the weight PDADMAC fraction from 0 to 0.2. The results indicated a great potential of the polymer-colloid formulations for the fabrication of structured sand coatings with controlled properties. Full article

The in situ synthesis of Fe⁰ particles using poly-(acrylic acid) (PAA) is an effective tool for fabricating catalytic membranes relevant to advanced oxidation processes (AOPs). Through their synthesis in polyelectrolyte multilayer-based nanofiltration membranes, it becomes possible to reject and degrade organic micropollutants simultaneously. In this work, we compare two approaches, where Fe⁰ nanoparticles are synthesized in or on symmetric multilayers and asymmetric multilayers. For the membrane with symmetric multilayers (4.0 bilayers of poly (diallyldimethylammonium chloride) (PDADMAC)/PAA), the in situ synthesized Fe⁰ increased its permeability from 1.77 L/m²/h/bar to 17.67 L/m²/h/bar when three Fe²⁺ binding/reducing cycles were conducted. Likely, the low chemical stability of this polyelectrolyte multilayer allows it to become damaged through the relatively harsh synthesis. However, when the in situ synthesis of Fe⁰ was performed on top of asymmetric multilayers, which consist of 7.0 bilayers of the very chemically stable combination of PDADMAC and poly(styrene sulfonate) (PSS), coated with PDADMAC/PAA multilayers, the negative effect of the Fe⁰ in situ synthesized can be mitigated, and the permeability only increased from 1.96 L/m²/h/bar to 2.38 L/m²/h/bar with three Fe²⁺ binding/reducing cycles. The obtained membranes with asymmetric polyelectrolyte multilayers exhibited an excellent naproxen treatment efficiency, with over 80% naproxen rejection on the permeate side and 25% naproxen removal on the feed solution side after 1 h. This work demonstrates the potential of especially asymmetric polyelectrolyte multilayers to be effectively combined with AOPs for the treatment of micropollutants (MPs). Full article

Biocidal compositions based on interpolyelectrolyte complexes and a low molecular weight antibiotic can become a promising material for creating biocidal coatings, as they combine wash-off resistance and dual biocidal action due to the biocide and the polycation. Molecular mass characteristics of polymers play an essential role in the physics and mechanical properties of the coatings. In this work, the properties of polydiallyldimethylammonium chloride (PDADMAC) coatings of various molecular weights are investigated and assumptions are made about the optimal molecular weight needed to create antibacterial compositions. To study the resistance to washing off and moisture saturation of the coatings, the gravimetric method was used, and the adhesive properties of the coatings were studied by dynamometry. It has been established that an increase in molecular weight affects the wash-off resistance of coatings, but does not affect moisture absorption and adhesion mechanics of coatings. All samples of PDADMAC were demonstrated to exhibit the same antibacterial activity. Thus, when developing systems for creating antibacterial coatings, it must be taken into account that in order to create stable coatings, the requirement to use PDADMAC with a high degree of polymerization is necessary for the coating desorption control during wash off-but not mandatory for the control of mechanical and antibacterial properties of the coating. Full article

Carrageenan is a polysaccharide of a plant origin, commonly used as a thickening and gelling agent in the food, pharmaceutical, and cosmetic industries. Due to the negative charges of its sulfate groups, carrageenan macromolecules strongly interact with oppositely charged polyions. The ionic complexes of carrageenan with poly(diallyldimethylammonium chloride) were obtained at the molar ratios 4:1, 2;1, 1:1, 1:2, and 1:4. The structure and characteristics of the polyanion-polycation associates were studied by XRD, IR, optical microscopy, and via sedimentation and particle size measurements. It was found that the suspended particles flocculate and settle fastest when the molar ratio of the polyions is near 1:1. Turbidimetric titration experiments enabled us to measure the molar ratio of cationic to anionic groups at the onset of flocculation, and the value in question was found to be 1:1.32. In other words, a mass of 511 mg carrageenan corresponds to one millimole of ester sulfate (monobasic) groups. The measurement of the onset of flocculation has been employed for the accurate determination of carrageenan in real samples of food products. The color and turbidity of the sample do not interfere with the determination results. Full article