Search Results (34)

This study examines the adsorption and bulk assembly behaviour of quaternized hydroxyethylcellulose ethoxylate (QHECE)–sodium dodecyl sulphate (SDS) complexes on negatively charged substrates. Due to its quaternized structure, QHECE, which is used in several industries, including cosmetics, exhibits enhanced electrostatic interactions. The phase behaviour and adsorption mechanisms of QHECE–SDS complexes are investigated using model substrates that mimic the wettability and surface charge of damaged hair fibres. Two preparation methodologies, high-concentration mixing and gradient-free mixing, were employed to examine their impact on the complex equilibrium, phase behaviour, and adsorption properties of the complexes. The measurements of turbidity, electrophoretic mobility, and conductivity demonstrate the existence of nonequilibrium dynamics during the mixing process, which exert a significant influence on the structural and functional characteristics of the complexes. The quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to investigate the adsorption of the complexes onto the substrates. The results demonstrated the critical role of intermediate SDS concentrations in enhancing deposition. The findings emphasise the importance of formulation and preparation protocols in designing stable, high-performance cosmetic products. This research advances our understanding of polyelectrolyte–surfactant interactions and provides insights into optimising QHECE-based formulations. Full article

The relevance of active research lies in the need to develop new technologies to improve drug delivery methods for the effective treatment of wound healing. Additionally, the potential application of organogels in other areas of biomedicine, such as creating medical patches with controlled drug delivery, indicates a wide range of possibilities for using this technology. This study focuses on developing controlled drug delivery systems using organogels as carriers for ceftriaxone and ofloxacin. By selecting optimal formulations, organogels were created to immobilize the drugs, facilitating their effective and sustained release. The swelling behavior of the hydrogels was studied, showing a swelling coefficient between 16 and 32%, indicating their ability to absorb liquid relative to their weight. Drug release studies demonstrated that ceftriaxone was released 1.8 times slower than ofloxacin, ensuring a more controlled delivery. Microbiological tests confirmed that the organogels containing ofloxacin exhibited antimicrobial activity against Escherichia coli, Bacillus subtilis, and Staphylococcus aureus. However, it was a challenge to estimate activity for the model antibiotic ceftriaxone due to bacterial resistance to it. Organogel poly(vinyl alcohol) (PVA)-DMSO–alginate modifications with surfactant cetylpyridinium bromide led to the formation of a polyelectrolyte complex on the interphase, allowing further enhanced the prolonged release of the drugs. The research identified that the optimal compositions for sustained drug release were organogels with compositions PVA (10%)-PVP (1%) DMSO (50%) and PVA (10%)-DMSO (50%) formulations, illustrating the transparent nature of these organogels making them suitable for ophthalmological application. Various organogels compositions (PVA-DMSO, PVA-poly(vinylpyrrolidone)-DMSO, PVA-DMSO–alginate, PVA-DMSO-PLGA, PVA-DMSO–drug–surfactant) loaded with ceftriaxone, ofloxacin, and surfactant were prepared and characterized, highlighting their potential use in antibiotic patches for wound healing. These organogels illustrate promising results for localized treatment of infections in wounds, cuts, burns, and other skin lesions. Full article

Polyelectrolyte–surfactant complexes (PESCs) have garnered significant attention due to their extensive range of biological and industrial applications. Most present applications are predominantly used in liquid or emulsion states, which limits their efficacy in solid material-based applications. Herein, pre-hydrolyzed polyacrylonitrile (HPAN) and quaternary ammonium salts (QAS) are employed to produce PESC electrospun membranes via electrospinning. The formation process of PESCs in a solution is observed. The results show that the degree of PAN hydrolysis and the varying alkyl chain lengths of surfactants affect the rate of PESC formation. Moreover, PESCs/PCL hybrid electrospun membranes are fabricated, and their antibacterial activities against both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) are investigated. The resulting electrospun membranes exhibit high bactericidal efficacy, which enables them to serve as candidates for future biomedical and filtration applications. Full article

Contemporary research concerning surfactant science and technology comprises a variety of requirements relating to the design of surfactant structures with widely varying architectures to achieve physicochemical properties and dedicated functionality. Such approaches are necessary to make them applicable to modern technologies, such as nanostructure engineering, surface structurization or fine chemicals, e.g., magnetic surfactants, biocidal agents, capping and stabilizing reagents or reactive agents at interfaces. Even slight modifications of a surfactant’s molecular structure with respect to the conventional single-head–single-tail design allow for various custom-designed products. Among them, multicharge structures are the most intriguing. Their preparation requires specific synthetic routes that enable both main amphiphilic compound synthesis using appropriate step-by-step reaction strategies or coupling approaches as well as further derivatization toward specific features such as magnetic properties. Some of the most challenging aspects of multicharge cationic surfactants relate to their use at different interfaces for stable nanostructures formation, applying capping effects or complexation with polyelectrolytes. Multiheaded cationic surfactants exhibit strong antimicrobial and antiviral activity, allowing them to be implemented in various biomedical fields, especially biofilm prevention and eradication. Therefore, recent advances in synthetic strategies for multiheaded cationic surfactants, their self-aggregation and performance are scrutinized in this up-to-date review, emphasizing their applications in different fields such as building blocks in nanostructure engineering and their use as fine chemicals. Full article

Objectives. This study was aimed at the investigation of the supramolecular systems based on cationic surfactants bearing cyclic head groups (imidazolium and pyrrolidinium) and polyanions (polyacrylic acid (PAA) and human serum albumin (HSA)), and factors governing their structural behavior to create functional nanosystems with controlled properties. Research hypothesis. Mixed PE–surfactant complexes based on oppositely charged species are characterized by multifactor behavior strongly affected by the nature of both components. It was expected that the transition from a single surfactant solution to an admixture with PE might provide synergetic effects on structural characteristics and functional activity. To test this assumption, the concentration thresholds of aggregation, dimensional and charge characteristics, and solubilization capacity of amphiphiles in the presence of PEs have been determined by tensiometry, fluorescence and UV-visible spectroscopy, and dynamic and electrophoretic light scattering. Results. The formation of mixed surfactant–PAA aggregates with a hydrodynamic diameter of 100–180 nm has been shown. Polyanion additives led to a decrease in the critical micelle concentration of surfactants by two orders of magnitude (from 1 mM to 0.01 mM). A gradual increase in the zeta potential of HAS–surfactant systems from negative to positive value indicates that the electrostatic mechanism contributes to the binding of components. Additionally, 3D and conventional fluorescence spectroscopy showed that imidazolium surfactant had little effect on HSA conformation, and component binding occurs due to hydrogen bonding and Van der Waals interactions through the tryptophan amino acid residue of the protein. Surfactant–polyanion nanostructures improve the solubility of lipophilic medicines such as Warfarin, Amphotericin B, and Meloxicam. Perspectives. Surfactant–PE composition demonstrated beneficial solubilization activity and can be recommended for the construction of nanocontainers for hydrophobic drugs, with their efficacy tuned by the variation in surfactant head group and the nature of polyanions. Full article

Mesoporous bioactive glass is a promising biomaterial for bone tissue engineering due to its good biocompatibility and bioactivity. In this work, we synthesized a hierarchically porous bioactive glass (HPBG) using polyelectrolyte-surfactant mesomorphous complex as template. Through the interaction with silicate oligomers, calcium and phosphorus sources were successfully introduced into the synthesis of hierarchically porous silica, and HPBG with ordered mesoporous and nanoporous structures was obtained. The morphology, pore structure and particle size of HPBG can be controlled by adding block copolymer as co-template or adjusting the synthesis parameters. The ability to induce hydroxyapatite deposition in simulated body fluids (SBF) demonstrated the good in vitro bioactivity of HPBG. Overall, this work provides a general method for the synthesis of hierarchically porous bioactive glasses. Full article

This work focuses on identifying and prioritizing factors that allow control of the properties of polyelectrolyte-surfactant complexes in two-phase microfluidic confinement and provide advantages over synthesis of such complexes in macroscopic conditions. We characterize the impact of polymer and surfactant aqueous flow conditions on the formation of microscale droplets and fluid threads in the presence of an immiscible organic solvent. We perform an experimental and selected numerical analysis of fast supramolecular reactions in droplets and threads. The work offers a quantitative control over properties of polyelectrolyte-surfactant complexes produced in two-phase confinement by varying capillary numbers and the ratio of aqueous and organic flowrates. We propose a combined thread-droplet mode to synthesize polyelectrolyte-surfactant complexes. This mode allows the production of complexes in a broader size range of R ≈ 70–200 nm, as compared with synthesis in macroscopic conditions and the respective sizes R ≈ 100–120 nm. Due to a minimized impact of undesirable post-chip reactions and ordered microfluidic confinement conditions, the dispersity of microfluidic aggregates (PDI = 0.2–0.25) is lower than that of their analogs synthesized in bulk (PDI = 0.3–0.4). The proposed approach can be used for tailored synthesis of target drug delivery polyelectrolyte-surfactant systems in lab-on-chip devices for biomedical applications. Full article

The goal of this work is to classify and quantify the factors that govern polyelectrolyte–surfactant complexation in microfluidic confinement and optimize the designs and operating modes of microfluidic reactors to offer additional advantages over the macroscopic synthesis of such complexes. We analyze and solve a system of governing convection–diffusion–reaction equations to conveniently represent these factors or their combinations as dimensionless similarity criteria. We discuss how these factors contribute to the on-chip control of the reaction initiation, the complex product distribution in a microfluidic device, and the phase behavior of the confined reacting flows and experimentally verify the results in microchips. This approach allows for designing microfluidic devices and setting their operating modes to avoid undesirable clogging by reaction products, control the initiation of the complexation reaction, and produce polyelectrolyte–surfactant aggregates with a broader size range and reduced dispersity. Full article

Extensive research is currently being conducted into novel ocular drug delivery systems (ODDS) that are capable of surpassing the limitations associated with conventional intraocular anterior and posterior segment treatments. Nanoformulations, including those synthesised from the natural, hydrophilic glycosaminoglycan, hyaluronic acid (HA), have gained significant traction due to their enhanced intraocular permeation, longer retention times, high physiological stability, inherent biocompatibility, and biodegradability. However, conventional nanoformulation preparation methods often require large volumes of organic solvent, chemical cross-linkers, and surfactants, which can pose significant toxicity risks. We present a comprehensive, critical review of the use of HA in the field of ophthalmology and ocular drug delivery, with a discussion of the physicochemical and biological properties of HA that render it a suitable excipient for drug delivery to both the anterior and posterior segments of the eye. The pivotal focus of this review is a discussion of the formation of HA-based nanoparticles via polyelectrolyte complexation, a mild method of preparation driven primarily by electrostatic interaction between opposing polyelectrolytes. To the best of our knowledge, despite the growing number of publications centred around the development of HA-based polyelectrolyte complexes (HA-PECs) for ocular drug delivery, no review articles have been published in this area. This review aims to bridge the identified gap in the literature by (1) reviewing recent advances in the area of HA-PECs for anterior and posterior ODD, (2) describing the mechanism and thermodynamics of polyelectrolyte complexation, and (3) critically evaluating the intrinsic and extrinsic formulation parameters that must be considered when designing HA-PECs for ocular application. Full article

Mixtures of polyelectrolytes and surfactants are commonly used in many technological applications where the challenge is to provide well-defined modifications of the surface properties, as is the case of washing formulations in cosmetics. However, if contemporary experimental and theoretical methods can provide insights on their behavior in concentrated formulations, less is known on their behavior under practical use conditions, e.g., under dilution and vectorization of deposits. This makes it difficult to make predictions for specific performance, as, for example, good hair manageability after a shampoo or a comfortable sensorial appreciation after a skin cleanser. This is especially important when considering the formulation of new, more eco-friendly formulations. In this work, a detailed study of the phase separation process induced by dilution is described, as well as the impact on the deposition of conditioning material on negatively charged surfaces. In order to gain a more detailed physical insight, several polyelectrolyte–surfactant pairs, formed by two different polymers and five surfactants that, although non-natural or eco-friendly, can be considered as models of classical formulations, have been studied. The results evidenced that upon dilution the behavior, and hence its deposition onto the surface, cannot be predicted in terms of the behavior of simpler pseudo-binary (mixtures of a polymer and a surfactant) or pseudo-ternary mixtures (two polymers and a surfactant). In many cases, phase separation was observed for concentrations similar to those corresponding to the components in some technological formulations, whereas the latter appeared as monophasic systems. Therefore, it may be assumed that the behavior in multicomponent formulations is the result of a complex interplay of synergistic interactions between the different components that will require revisiting when new, more eco-sustainable ingredients are considered. Full article

Chitosan (Chi) and 77KS, a lysine-derived surfactant, form polyelectrolyte complexes that reverse their charge from positive to negative at higher 77KS concentrations, forming aggregates that have been embedded with amoxicillin (AMOX). Dispersion of this complex was used to coat polydimethylsiloxane (PDMS) films, with an additional layer of anionic and hydrophilic hyaluronic acid (HA) as an outer adsorbate layer to enhance protein repulsion in addition to antimicrobial activity by forming a highly hydrated layer in combination with steric hindrance. The formed polysaccharide-based bilayer on PDMS was analyzed by water contact angle measurements, X-ray photoelectron spectroscopy (XPS), and surface zeta (ζ)-potential. All measurements show the existence and adhesion of the two layers on the PDMS surface. Part of this study was devoted to understanding the underlying protein adsorption phenomena and identifying the mechanisms associated with biofouling. Thus, the adsorption of a mixed-protein solution (bovine serum albumin, fibrinogen, γ-globulin) on PDMS surfaces was studied to test the antifouling properties. The adsorption experiments were performed using a quartz crystal microbalance with dissipation monitoring (QCM-D) and showed improved antifouling properties by these polysaccharide-based bilayer coatings compared to a reference or for only one layer, i.e., the complex. This proves the benefit of a second hyaluronic acid layer. Microbiological and biocompatibility tests were also performed on real samples, i.e., silicone discs, showing the perspective of the prepared bilayer coating for medical devices such as prostheses, catheters (balloon angioplasty, intravascular), delivery systems (sheaths, implants), and stents. Full article

Oppositely charged polymer–surfactant complexes are frequently explored as a function of phase space defined by the charge ratio Z, (where Z = [${+}_{polymer}]/\left[{-}_{surfactant}\right]$), commonly accessed through the surfactant concentration. Tuning the phase behaviour and related properties of these complexes is an important tool for optimising commercial formulations; hence, understanding the relationship between Z and bulk properties is pertinent. Here, within a homologous series of cationic hydroxyethyl cellulose (cat-HEC) polymers with minor perturbations in the degree of side chain charge modification, phase space is instead explored through $\left[{+}_{polymer}\right]$ at fixed C${}_{polymer}$. The nanostructures were characterised by small-angle neutron scattering (SANS) in D${}_2$O solutions and in combination with the oppositely charged surfactant sodium dodecylsulfate (h- or d-SDS). Scattering consistent with thin rods with an average radius of ∼7.7 Å and length of ∼85 Å was observed for all cat-HEC polymers and no significant interactions were shown between the neutral HEC polymer and SDS (C${}_{SDS}$ < CMC). For the charge-modified polymers, interactions with SDS were evident and the radius of the formed complexes grew up to ∼15 Å with increasing Z. This study demonstrates a novel approach in which the Z phase space of oppositely charged polymer–surfactant complexes can be controlled at fixed concentrations. Full article

The formation of coffee-ring deposits upon evaporation of sessile droplets containing mixtures of poly(diallyldimethylammonium chloride) (PDADMAC) and two different anionic surfactants were studied. This process is driven by the Marangoni stresses resulting from the formation of surface-active polyelectrolyte–surfactant complexes in solution and the salt arising from the release of counterions. The morphologies of the deposits appear to be dependent on the surfactant concentration, independent of their chemical nature, and consist of a peripheral coffee ring composed of PDADMAC and PDADMAC–surfactant complexes, and a secondary region of dendrite-like structures of pure NaCl at the interior of the residue formed at the end of the evaporation. This is compatible with a hydrodynamic flow associated with the Marangoni stress from the apex of the drop to the three-phase contact line for those cases in which the concentration of the complexes dominates the surface tension, whereas it is reversed when most of the PDADMAC and the complexes have been deposited at the rim and the bulk contains mainly salt. Full article

In this work, we report the phase behavior of polyelectrolyte complex coacervates (PECs) of poly(acrylate) (PA⁻) and poly(diallyldimethylammonium) (PDADMA⁺) in the presence of inorganic salts. Titrations of the polyelectrolytes in their acidic and alkaline forms were performed to obtain the coacervates in the absence of their small counterions. This approach was previously applied to the preparation of polymer–surfactant complexes, and we demonstrate that it also succeeded in producing complexes free of small counterions with a low extent of Hofmann elimination. For phase behavior studies, two different molar masses of poly(acrylate) and two different salts were employed over a wide concentration range. It was possible to define the regions at which associative and segregative phase separation take place. The latter one was exploited in more details because the segregation phenomenon in mixtures of oppositely charged polyelectrolytes is scarcely reported. Phase composition analyses showed that there is a strong segregation for both PA⁻ and PDADMA⁺, who are accompanied by their small counterions. These results demonstrate that the occurrence of poly-ion segregation in these mixtures depends on the anion involved: in this case, it was observed with NaCl, but not with Na₂SO₄. Full article

In this paper, we report the development of the novel self-assembling systems based on oppositely charged Pillar[5]arenes and surfactants for encapsulation of diagnostic dye DAPI. For this purpose, the aggregation behavior of synthesized macrocycles and surfactants in the presence of Pillar[5]arenes functionalized by carboxy and ammonium terminal groups was studied. It has been demonstrated that by varying the molar ratio in Pillar[5]arene-surfactant systems, it is possible to obtain various types of supramolecular systems: host–guest complexes at equimolar ratio of Pillar[5]arene-surfactant and interpolyelectrolyte complexes (IPECs) are self-assembled materials formed in aqueous medium by two oppositely charged polyelectrolytes (macrocycle and surfactant micelles). It has been suggested that interaction of Pillar[5]arenes with surfactants is predominantly driven by cooperative electrostatic interactions. Synthesized stoichiometric and non-stoichiometric IPECs specifically interact with DAPI. UV-vis, luminescent spectroscopy and molecular docking data show the structural feature of dye-loaded IPEC and key role of the electrostatic, π–π-stacking, cation–π interactions in their formation. Such a strategy for the design of supramolecular Pillar[5]arene-surfactant systems will lead to a synergistic interaction of the two components and will allow specific interaction with the third component (drug or fluorescent tag), which will certainly be in demand in pharmaceuticals and biomedical diagnostics. Full article