Search Results (40)

There is a strong global demand for sulfate-free personal cleansing products. The objective of sulfate-free personal cleansing technology should not be aimed solely at the absence of “sulfate” wording in the list of ingredients, but on the true benefits both in personal use and in environmental effects. These include but are not limited to safety, mildness, and sensory effect for the individual and renewability, low carbon footprint, low water footprint, biodegradability, and sustainability for the environment. In addition, some surfactants or their precursors contain 1,4-dioxane as a by-product of their manufacturing, which is a major safety concern. This paper will deal with sulfate-free cleansing in two parts. Part I will examine the issues surrounding sulfates. Part II will show the benefits of amino acid-based surfactants for cleansing products, and specifically show why glutamates and alaninates are the best choices for safer and more efficacious cleansing. Several metrics will be included to support these conclusions. Full article

Background/Objectives: Cationic surfactants are potential antimicrobial candidates. Even so, they are the foremost irritative and incompatible group, which limits their usage. The incorporation of surfactants in biopolymer-based nanoparticles is a feasible strategy to improve their efficacy and reduce those drawbacks. Methods: Surfactants with one amino acid on the polar head (lauroyl arginine methyl ester—LAM and phenylalanine dodecyl amide—PNHC₁₂) and surfactants with two amino acids on the polar heads, arginine-phenylalanine (Lauroyl phenylalanine arginine methyl esther—C₁₂PAM and phenylalanine-arginine dodecyl amide—PANHC₁₂) were loaded to zein nanoparticles. Their antimicrobial and antibiofilm activities were evaluated. Also, the inhibitory activities of the surfactants and nanoparticles over skin-related enzymes were accessed in silico and in vitro, while their cytotoxicity was determined comparatively over immortal human keratinocytes (HaCaT) and human fibroblasts (3T3). Finally, the Vibrio fisheri luminescence reduction test was used to detect its ecotoxicity. Results: The nanoparticles were obtained successfully and exhibited good biocide activity against a wide range of pathogenic bacteria and yeasts. The surfactants were found active over the enzymes assayed: elastase > tyrosinase > collagenase > lipoxygenase, while the inhibitory activity was superior when nanoencapsulated over the enzymes tyrosinase and lipoxygenase. The surfactants and their corresponding nanoparticles presented acceptable cytotoxic levels, except for PNHC₁₂ in both forms, while their ecotoxicity was limited and acceptable. Conclusions: Accordingly, the nanoencapsulation of the arginine-phenylalanine surfactants loaded to zein nanoparticles was found to be a smart strategy to enhance the antimicrobial activity and improve their selectivity over representative skin and connective tissues cell lines. These biological properties render the arginine-phenylalanine surfactant nanoparticles as promising candidates for antimicrobial and tissue repairing applications in wound treatments. Full article

Electrical conductimetry and dynamic light scattering (DLS) were used to investigate the aggregation behaviors of four amino acid-based surfactants (AABSs; undecanoyl-glycine, undecanoyl-l-alanine, undecanoyl-l-valine, undecanoyl-l-leucine) in the presence of five linear diamine counterions (1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane). Electrical conductimetry was used to measure the CMCs for each system, which ranged from 5.1 to 22.5 mM. With respect to counterions, the obtained CMCs decreased with increases in the interamine spacer length; this was attributed to the improved torsional binding flexibility in longer counterions. Strong linear correlations (mean R² = 0.9443) were observed between the CMCs and predicted surfactant partition coefficients (logP; water/octanol), suggesting that micellization is primarily driven by the AABS’s hydrophobicity for these systems. However, significant deviations in this linear relationship were observed for systems containing 1,2-diaminoethane, 1,4-diaminobutane, and 1,6-diaminohexane (p = 0.0774), suggesting altered binding dynamics for these counterions. pH measurements during the CMC determination experiments indicated the full deprotonation of the AABSs but did not give clear insights into the counterion protonation states, thus yielding an inconclusive evaluation of their charge stabilization effects during binding. However, DLS measurements revealed that the micellar size remained largely independent of the counterion length for counterions longer than 1,2-diaminoethane, with hydrodynamic diameters ranging from 2.2 to 2.8 nm. This was explained by the formation of charge-stabilized noncovalent dimers, with each counterion bearing a full +2 charge. Conductimetry-based estimates of the degrees of counterion binding (β) and free energies of micellization (ΔG°_M) revealed that bulky AABSs exhibit preferential binding to counterions with an even number of methylene groups. It is proposed that when these counterions form noncovalent dimers, perturbations in their natural geometries result in the formation of a binding pocket that accommodates the AABS steric bulk. While the direct application of these systems remains to be seen, this study provides valuable insights into the structure–property relationships that govern AABS aggregation. Full article

Tight reservoirs, characterized by low porosity, low permeability, and difficulty in fluid flow, rely on horizontal wells and large-scale hydraulic fracturing for development. During fracturing, a significant volume of fracturing fluid is injected into the reservoir at a rate far exceeding its absorption capacity. This not only serves to create fractures but also impacts the recovery efficiency of tight reservoirs. Therefore, achieving the integration of fracturing and enhanced recovery functions within the working fluid (fracturing-enhanced recovery integration) becomes particularly crucial. This study describes the concept and characteristics of fracturing-enhanced recovery integration and analyzes the types and features of working fluids. We also discuss the challenges and prospects faced by these fluids. Working fluids for fracturing-enhanced recovery integration need to consider the synergistic effects of fracturing and recovery; meet the performance requirements during fracturing stages such as fracture creation, proppant suspension, and flowback; and also address the demand for increased recovery. The main mechanisms include (1) enlarging the effective pore radius, (2) super-hydrophobic effects, and (3) anti-swelling properties. Fracturing fluids are pumped into fractures through pipelines, where they undergo complex flow in multi-scale fractures, ultimately seeping through capillary bundles. Flow resistance is influenced by the external environment, and the sources of flow resistance in fractures of different scales vary. Surfactants with polymerization capabilities, biodegradable and environmentally friendly bio-based surfactants, crosslinking agents, and amino acid-based green surfactants with outstanding properties will unleash their application potential, providing crucial support for the effectiveness of fracturing-enhanced recovery integration working fluids. This article provides important references for the green, efficient, and sustainable development of tight oil reservoirs. Full article

Background: This work proposes the development of new vesicular systems based on anesthetic compounds (lidocaine (LID) and capsaicin (CA)) and antimicrobial agents (amino acid-based surfactants from phenylalanine), with a focus on physicochemical characterization and the evaluation of antimicrobial and cytotoxic properties. Method: Phenylalanine surfactants were characterized via high-performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR). Different niosomal systems based on capsaicin, lidocaine, cationic phenylalanine surfactants, and dipalmitoyl phosphatidylcholine (DPPC) were characterized in terms of size, polydispersion index (PI), zeta potential, and encapsulation efficiency using dynamic light scattering (DLS), transmitted light microscopy (TEM), and small-angle X-ray scattering (SAXS). Furthermore, the interaction of the pure compounds used to prepare the niosomal formulations with DPPC monolayers was determined using a Langmuir balance. The antibacterial activity of the vesicular systems and their biocompatibility were evaluated, and molecular docking studies were carried out to obtain information about the mechanism by which these compounds interact with bacteria. Results: The stability and reduced size of the analyzed niosomal formulations demonstrate their potential in pharmaceutical applications. The nanosystems exhibit promising antimicrobial activity, marking a significant advancement in pharmaceutical delivery systems with dual therapeutic properties. The biocompatibility of some formulations underscores their viability. Conclusions: The proposed niosomal formulations could constitute an important advance in the pharmaceutical field, offering delivery systems for combined therapies thanks to the pharmacological properties of the individual components. Full article

NMR spectroscopy, molecular modeling, and conductivity experiments were used to investigate micelle formation by the amino acid-based surfactant tridecanoic L-glutamic acid. Amino acid-based biosurfactants are green alternatives to surfactants derived from petroleum. NMR titrations were used to measure the monomeric surfactant’s primary and gamma (γ) carboxylic acid pK_a values. Intramolecular hydrogen bonding within the surfactant’s headgroup caused the primary carboxylic acid to be less acidic than the corresponding functional group in free L-glutamic acid. Likewise, intermolecular hydrogen bonding caused the micellar surfactant’s γ carboxylic functional group to be less acidic than the corresponding monomer value. The binding of four positive counterions to the anionic micelles was also investigated. At pH levels below 7.0 when the surfactant headgroup charge was −1, the micelle hydrodynamic radii were larger (~30 Å) and the mole fraction of micelle-bound counterions was in the 0.4–0.7 range. In the pH range of 7.0–10.5, the micelle radii decreased with increasing pH and the mole fraction of micelle bound counterions increased. These observations were attributed to changes in the surfactant headgroup charge with pH. Above pH 10.5, the counterions deprotonated and the mole fraction of micelle-bound counterions decreased further. Finally, critical micelle concentration measurements showed that the micelles formed at lower concentrations at pH 6 when the headgroup charge was predominately −1 and at higher concentrations at pH 7 where headgroups had a mixture of −1 and −2 charges in solution. Full article

In this study, a series of four surface-active compounds—N-alkyl betaine ethyl ester chlorides, C_nBetC₂Cl—were synthesized and characterized in aqueous solutions. As with other alkyl betaines, these amphiphiles can be practically used, for example, as co-surfactants and/or solubility enhancers acting according to hydrotropic or micellar mechanisms, depending on the alkyl chain length in the amine. We focused on the representatives of the medium alkyl chain length (C₆–C₁₂) to find the dependence between the alkyl chain length in N-alkyl betaine ethyl ester chlorides and the surface, volumetric, acoustic, and viscometric properties of their solutions. Ethyl esters, the derivatives of amino acids, were chosen to increase functionality and take advantage of possible hydrolysis in solutions at higher pH, which is also a key parameter in biodegradability. The micellization parameters were calculated based on the physicochemical characteristics. We focused our interest on the ester with a dodecyl substituent since we can compare and discuss its properties with some other C₁₂ representatives that are available in literature. Surprisingly, its micellization characteristic is almost temperature-independent in the investigated temperature range, t = (15–45) °C. Particularly interesting are the results of dynamic light scattering (DLS), which show that the changes in physicochemical parameters of the C₁₂ homolog around the CMC are caused by the two types of micelles of different sizes present in solutions. Full article

The physical properties of sodium cocoyl glycinate (SCG) and the synergistic effects within the SCG/CAPB complex system were investigated using visible–ultraviolet spectrophotometry and a surface tension meter. Analysis of the synergistic parameters of the complex system revealed that the combination of SCG and cocamidopropyl betaine (CAPB) yielded superior results compared to the individual use of SCG. Building upon this, the ternary phase behavior of the SCG/CAPB/H₂O system was further explored. Different lyotropic liquid crystal phases were identified using polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). Surfactant solutions with varying mass fractions exhibited diverse phase behaviors, including the micellar phase (L₁), micelle–solid mixed phase (L₁-S), hexagonal phase (H), and lamellar phase (L_α), with the insoluble solid phase predominating. The investigation of the ternary phase diagram of SCG/CAPB/H₂O provided valuable guidance for detergent formulation screening, enriched the understanding of sodium cocoyl glycinate complex systems, and further promoted the utilization of amino acid-based surfactants in the field of personal care products. Full article

Carboranes are promising agents for applications in boron neutron capture therapy (BNCT), but their hydrophobicity prevents their use in physiological environments. Here, by using reverse docking and molecular dynamics (MD) simulations, we identified blood transport proteins as candidate carriers of carboranes. Hemoglobin showed a higher binding affinity for carboranes than transthyretin and human serum albumin (HSA), which are well-known carborane-binding proteins. Myoglobin, ceruloplasmin, sex hormone-binding protein, lactoferrin, plasma retinol-binding protein, thyroxine-binding globulin, corticosteroid-binding globulin and afamin have a binding affinity comparable to transthyretin/HSA. The carborane@protein complexes are stable in water and characterized by favorable binding energy. The driving force in the carborane binding is represented by the formation of hydrophobic interactions with aliphatic amino acids and BH-π and CH-π interactions with aromatic amino acids. Dihydrogen bonds, classical hydrogen bonds and surfactant-like interactions also assist the binding. These results (i) identify the plasma proteins responsible for binding carborane upon their intravenous administration, and (ii) suggest an innovative formulation for carboranes based on the formation of a carborane@protein complex prior to the administration. Full article

Highly efficient silicone surfactants are typically based on polyether hydrophiles. As part of a program to increase the natural content of silicones, we describe the synthesis of silicone surfactants with amino acid hydrophiles (cysteine, arginine, and lysine). The compounds were prepared using a radial thiol–ene reaction with vinylsilicones for cysteine derivatives and a catalyst-free aza-Michael reaction with arginine and lysine. Short chain surfactants with silicone monomer:hydrophile ratios of 5:1 or less (e.g., telechelic silicones of lysine-linker-(Me₂OSi)_n-linker-lysine n = 10) were ineffective at stabilizing emulsions of silicone oil (D₄): water. However, excellent surfactants were realized as the chain length (n) increased to 25 or 50, stabilizing water-in-oil emulsions with high water content (80% or 90%). The surfactants, especially the longer chain compounds, were stable against pH except <4 or >9 and survived freeze/thaw cycles. These surfactants contain 12–25% natural materials, improving their sustainability compared to those containing synthetic hydrophiles. Full article

The binding of linear diamine counterions with different methylene chain lengths to the amino-acid-based surfactants undecanoic L-isoleucine (und-IL) and undecanoic L-norleucine (und-NL) was investigated with NMR spectroscopy. The counterions studied were 1,2-ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. These counterions were all linear diamines with varying spacer chain lengths between the two amine functional groups. The sodium counterion was studied as well. Results showed that when the length of the counterion methylene chain was increased, the surfactants’ critical micelle concentrations (CMC) decreased. This decrease was attributed to diamines with longer methylene chains binding to multiple surfactant monomers below the CMC and thus acting as templating agents for the formation of micelles. The entropic hydrophobic effect and differences in diamine counterion charge also contributed to the size of the micelles and the surfactants’ CMCs in the solution. NMR diffusion measurements showed that the micelles formed by both surfactants were largest when 1,4-diaminobutane counterions were present in the solution. This amine also had the largest mole fraction of micelle-bound counterions. Finally, the und-NL micelles were larger than the und-IL micelles when 1,4-diaminobutane counterions were bound to the micelle surface. A model was proposed in which this surfactant formed non-spherical aggregates with both the surfactant molecules’ hydrocarbon chains and n-butyl amino acid side chains pointing toward the micelle core. The und-IL micelles, in contrast, were smaller and likely spherically shaped. 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

Water-in-oil (w/o) nanoemulsions stabilized with amino acid surfactants (AAS) are one example of nanotechnology detergents of the “brush on, wipe off”-type for removing graffiti coatings from different sensitive surfaces. The high-pressure homogenization (HPH) process was used to obtain the nanostructured fluids (NSFs), including the non-toxic and eco-friendly components such as AAS, esterified vegetable oils, and ethyl lactate. The most effective NSF detergent was determined by response surface methodology (RSM) optimization. Afterwards, several surface properties, i.e., topography, wettability, surface free energy, and the work of water adhesion to surfaces before and after their coverage with the black graffiti paint, as well as after the removal of the paint layers by the eco-remover, were determined. It was found that the removal of graffiti with the use of the NSF detergent is more dependent on the energetic properties and microporous structure of the paint coatings than on the properties of the substrates on which the layers were deposited. The use of NSFs and knowledge of the surface properties could enable the development of versatile detergents that would remove unwanted contamination from various surfaces easily and in a controlled way. Full article

Mixtures of cationic and anionic surfactants often originate bilayer structures, such as vesicles and lamellar liquid crystals, that can be explored as model membranes for fundamental studies or as drug and gene nanocarriers. Here, we investigated the aggregation properties of two catanionic mixtures containing biomimetic surfactants derived from serine. The mixtures are designated as 12Ser/8-8Ser and 14Ser/10-10Ser, where mSer is a cationic, single-chained surfactant and n-nSer is an anionic, double-chained one (m and n being the C atoms in the alkyl chains). Our goal was to investigate the effects of total chain length and chain length asymmetry of the catanionic pair on the formation of catanionic vesicles, the vesicle properties and the vesicle/micelle transitions. Ocular observations, surface tension measurements, video-enhanced light microscopy, cryogenic scanning electron microscopy, dynamic and electrophoretic light scattering were used to monitor the self-assembly process and the aggregate properties. Catanionic vesicles were indeed found in both systems for molar fractions of cationic surfactant ≥0.40, always possessing positive zeta potentials (ζ = +35–50 mV), even for equimolar sample compositions. Furthermore, the 14Ser/10-10Ser vesicles were only found as single aggregates (i.e., without coexisting micelles) in a very narrow compositional range and as a bimodal population (average diameters of 80 and 300 nm). In contrast, the 12Ser/8-8Ser vesicles were found for a wider sample compositional range and as unimodal or bimodal populations, depending on the mixing ratio. The aggregate size, pH and zeta potential of the mixtures were further investigated. The unimodal 12Ser/8-8Ser vesicles (<D_H> ≈ 250 nm, pH ≈ 7–8, ζ ≈ +32 mV and a cationic/anionic molar ratio of ≈2:1) are particularly promising for application as drug/gene nanocarriers. Both chain length asymmetry and total length play a key role in the aggregation features of the two systems. Molecular insights are provided by the main findings. Full article

Although cationic surfactants have a remarkable antimicrobial activity, they present an intrinsic toxicity that discourages their usage. In this work novel zein nanoparticles loaded with arginine-phenylalanine-based surfactants are presented. The nanoparticles were loaded with two single polar head (LAM and PNHC₁₂) and two with double amino acid polar head surfactants, arginine-phenylalanine (C₁₂PAM, PANHC₁₂). The formulations were characterized and their stability checked up to 365 days. Furthermore, the antimicrobial and hemolytic activities were investigated. Finally, NMR and molecular docking studies were carried out to elucidate the possible interaction mechanisms of surfactant-zein. The nanoparticles were obtained with satisfactory size, zeta potential and dispersibility. The surfactants containing arginine-phenylalanine residues were found to be more stable. The nanoencapsulation maintained the antimicrobial activities unaltered in comparison to the surfactants’ solutions. These results are in agreement with the NMR and docking findings, suggesting that zein interacts with the surfactants by the aromatic rings of phenylalanine. As a result, the cationic charges and part of the aliphatic chains are freely available to attack the bacteria and fungi, while not available to disrupt the cellular membranes. This approach opens new possibilities for using cationic surfactants and benefits from their extraordinary antimicrobial responses for several applications. Full article