Colloids Interfaces, Volume 6, Issue 2 (June 2022) – 21 articles

Surfactants present in cleansing formulations interact not only with the unwanted lipids accumulating on the human skin (dirt) but also with its protective lipidic layer (sebum). Development of simple models of human sebum would help to compare different surfactants and biosurfactants under the same conditions. In this contribution we propose a first monolayer model of synthetic sebum composed of lard, stearic acid, lanolin, squalane and cholesterol. The monolayer compression isotherm features a gas-liquid (G-LE1), two liquid-liquid transitions (LE1-LE2 and LE2-LC), and a collapse at π_coll = 45 mN/m. The monolayer spread on pure water and pre-compressed to π₀ = 30 mN/m was exposed to four synthetic surfactants (sodium lauryl sulfate (SLS), sodium laureth sulfate (SLES), ammonium lauryl sulfate (ALS) and cocamidopropyl betaine (CAPB)) and four plant extracts (oat (Avena sativa L.), horse chestnut (Aesculus hippocastanum L.), cowherb (Vaccaria hispanica [P. Mill.] Rauschert), soybean (Glycine max L.) and soapwort (Saponaria officinalis L.)) introduced to the subphase at a dry mass content of 1% (w/w). Three modes of the monolayer-(bio)surfactant interactions were observed: (1) complete solubilization (SLS, SLES, ALS, CAPB); (2) penetration accompanied by an increase of surface pressure and elasticity but without solubilization (horse chestnut, cowherb, soapwort); (3) no interaction (oat, soybean). Full article

Patterns of assembled colloidal particles can form on substrates due to solvent evaporation, and here we studied such phenomena in the drying of monodispersed colloidal hydrochar dispersions prepared by the hydrothermal carbonization of glucose and purified by dialysis. During the evaporation of water, line patterns or, in some cases, mud-like patterns formed. The line formation was investigated as a function of the pH of the dispersion, substrate shape, particle concentration, and concentration of sodium dodecylsulfate (SDS). The lines comprised dense assemblies of hydrochar particles. The line width increased with the successive evaporation of water. Sharper lines formed with the addition of SDS, which was ascribed to the effects of solubilization or moderated interactions. At greater particle concentrations, we also observed a continuous layer of colloidal particles between the lines. A mechanism for the line pattern formation derived from the literature on other colloids was proposed. Mud-like patterns formed on the substrate in concentrated samples without SDS addition and were put in the context of the formation of cracks in the drying of colloidal coatings. Hydrochars belong to carbon-rich colloids, which are of fundamental and technological importance. This research could be useful for in situ line printing within microfluidic devices, for example. Full article

This research is focused on the adsorption modification of detonation nanodiamond surfaces with antibiotics for their further use as smart materials for cardiovascular surgery purposes, namely as bioprostheses modifiers. Tritium-labeled amikacin and levofloxacin were used as tracers for the adsorption process control. We found that nanodiamonds form adsorption complexes with levofloxacin via physical adsorption, while in the case of amikacin, electrostatic attraction contributes to the formation of more stable complexes, even in the presence of electrolytes and desorbing agents (models of biological fluids). Antimicrobial characterization of nanodiamond–levofloxacin and nanodiamond–amikacin complexes indicates a reduction in the dose of antibiotics that is used as an antimicrobial agent. Therefore, the use of biomaterial based on DND complexes with antibiotics as the basis of bioprostheses will allow one either to avoid or significantly reduce the duration and intensity of antibiotics use in the postoperative period, which is critically important from the viewpoint of the development of antibiotic resistance in pathogens. Full article

A novel method is proposed for calculating the solvent flux density and electric current density in the process of flow of an electrolyte solution through a charged porous layer (membrane) under the simultaneous action of external pressure and electric potential gradients. The method is based on irreversible thermodynamics and the cell model of an ion-exchange membrane. It is shown that, with the increase in the electrolyte concentration, the total permeability of the porous structure also increases as a result of both barofiltration and electroosmotic transfer of the solvent when both external gradients are co-directional vectors. As for the current density, it also increases with the increasing electrolyte concentration owing to the growth of the streaming current and specific conductivity. Full article

Nanofluids have attracted significant research interest for their promising application in enhanced oil recovery. One striking feature leading to the outstanding efficiency of nanofluids in enhanced oil recovery is the structure of nanoparticles, which induces oscillatory structural forces in the confined space between fluid–fluid interfaces or air–liquid and liquid–solid interfaces. To promote the understanding of the oscillatory structural forces and their application in enhanced oil recovery, we reviewed the origin and theory of the oscillatory structural forces, factors affecting their magnitude, and the experimental techniques demonstrating their impacts on enhanced oil recovery. We also reviewed the methods, where the benefits of nanofluids in enhanced oil recovery provided by the oscillatory structural forces are directly manifested. The oscillatory structural forces promote the wetting and spreading of nanofluids on solid surfaces, which ultimately enhances the separation of oil from the reservoir. Some imbibition tests demonstrated as much as 50% increased oil recovery, compared to the cases where the oscillatory structural forces were absent. Full article

In this work, the conditions for the synthesis of open vase-like microcapsules with a size of 1–5 μm and 20–40 nm walls of NiFe_0.3(OH)_x layered double hydroxide were studied. These microcapsules were obtained by the rapid hydrolysis of microdroplets of a solution of a mixture of NiSO₄ and FeSO₄ salts at the surface of an alkali solution. A hypothetical model of successive chemical processes occurring at the interface during synthesis is presented. The features of the “rim” formation around each microcapsule hole from the wall material with a peculiar nozzle-like shape are noted. These microcapsules can be transferred to the surface of a nickel foil using the Langmuir–Schaefer (LS) method. During the transfer process, they are fixed to the surface in an oriented position with a “rim” that contacts the nickel surface. It was established that electrodes made of such a foil with a layer of microcapsules exhibit active electrocatalytic properties in the oxygen evolution reaction during the electrolysis of water in an alkaline medium. Full article

The review covers the research on thermocapillary convection caused by the thermal action of laser radiation in single-layer and bilayer liquid systems of capillary thickness. The advantages of using optical radiation are the instantaneous delivery of thermal energy to a place on demand (a bulk phase, interfaces); low radiation power required; concentrating heat flux on a spot of a few micrometers; the production of arbitrary spatial distributions of radiation intensity; and, as a result, corresponding thermal fields at a liquid interface and their fast reconfiguration. Thermocapillary stresses at the liquid interfaces lead to the transfer of the liquid and a change in the shape of the interface, in accordance with the distribution of the light-induced thermal field. Studies concerned with the methods of non-destructive testing of liquid media and solids, which are based on a photothermocapillary signal emitted by a laser-induced concave deformation of a thin layer, are considered. Features of thermocapillary deformation of a liquid–air interface caused by local heating of thin and thick (exceeding the capillary length) layers are demonstrated. A part of the review addresses the results of the study of thermocapillary rupture of films in the heating zone and the application of this effect in semiconductor electronics and high-resolution lithography. The works on the light-induced thermocapillary effect in bilayer (multilayer) liquid systems are analyzed, including early works on image recording liquid layer systems, liquid IR transducers, and nonlinear optical media. Full article

Optical switches in lipid membranes are an emerging tool to tune the properties of the bilayer or membrane protein integrated therein. Here, we use simple geometry and physics considerations to deduce structural criteria to design efficient photoactivated switches for lipid membranes. We compare how the area of projection on the bilayer of various classes of photoswitches changes upon the trans/cis or open/closed transition and show that azobenzene and stilbene should distort the bilayer structure the most. We also conclude that planar-elongated molecules, in which atoms of isomerizable double bond have no additional substituents, while substituents of the fragments adjacent to the double bond prevent formation of the planar molecule in cis configuration, are to be the best photoswitches for lipid membranes. Full article

Prussian blue nanozymes exhibit peroxidase-like catalytic activity and are therefore considered a stable and inexpensive alternative to natural peroxidases in the enzyme-linked immunosorbent assay (ELISA). In this work, we propose a robust method of Prussian blue nanozyme functionalization, which relies on the entrapment of nanozymes into albumin nanoparticles. The principle of the method is the addition of ethanol to a solution that contains albumin and nanozymes. At a high ethanol concentration solubility of albumin decreases, resulting in the formation of albumin nanoparticles loaded with nanozymes. The hydrodynamic diameter of nanoparticles was between 120 and 230 nm and depended on the nanozyme-to-BSA ratio. Encapsulation efficiency of nanozymes reached 96–99% and up to 190 μg of nanozymes were loaded per 1 mg of nanoparticles. Nanoparticles were stable at pH 5.5–7.5 and upon long-term storage in deionized water. Excellent reproducibility of the synthesis procedure was confirmed by the preparation of three individual batches of Prussian-blue-loaded BSA nanoparticles with almost identical properties. Nanoparticles were functionalized with monoclonal antibodies using glutaraldehyde cross-linking. The resulting conjugates were applied as labels in an ELISA-like assay of tumor marker prostate-specific antigen (PSA). The lower limit of detection was below 1 ng/mL, which enables measurement of PSA in the range of clinically relevant concentrations. Full article

The application of surface rheology and Brewster angle microscopy on mixed monolayers of DPPC and polymeric nanoparticles (cationic and anionic) showed that the sign of the particle charge affects the dynamic properties of the monolayers less than the nanoparticles’ ability to aggregate. Under almost physiological conditions, the effect of nanoparticles on the elasticity of DPPC monolayer is insignificant. However, the particles prevent the surface tension from decreasing to extremely low values. This effect could affect the functionality of pulmonary surfactants. Full article

Pickering emulsions stabilized by the interaction of palmitic acid (PA) and silica nanoparticles (SiNPs) at the water/oil interface have been studied using different alkane oil phases. The interaction of palmitic acid and SiNPs has a strong synergistic character in relation to the emulsion stabilization, leading to an enhanced emulsion stability in relation to that stabilized only by the fatty acid. This results from the formation of fatty acid-nanoparticle complexes driven by hydrogen bond interactions, which favor particle attachment at the fluid interface, creating a rigid armor that minimizes droplet coalescence. The comparison of emulsions obtained using different alkanes as the oil phase has shown that the hydrophobic mismatch between the length of the alkane chain and the C16 hydrophobic chain of PA determines the nature of the emulsions, with the solubility of the fatty acid in the oil phase being a very important driving force governing the appearance of phase inversion. Full article

This study mainly focused on the emulsifying performance of Limnophila aromatica crude extracts obtained by using different ethanolic aqueous solutions (0, 25, 50, 75, and 99.5% (v/v)). All Limnophila aromatica extracts (LAEs) were able to produce emulsions with a volume mean droplet diameter (d_4,3) ranging from 273 to 747 nm, except for LAE-99.5 (3269 nm). Only the emulsion prepared by LAE-75 was stable during seven days of storage, without significantly changing droplet size (479–495 nm). The result showed that all LAEs could reduce interfacial tension varied within 12.5 and 16.1 mN/m at the soybean oil/extracts (1% w/w) interface. Compared to other extracts, LAE-75 did not contain the highest protein, saponin, and phenol content (4.36%, 20.14%, and 11.68%, respectively), but it had the lowest ash content (14.74%). These results indicated that the emulsifying performance of LAEs did not rely only on interfacial tension and/or surface-active compounds. The residual demulsifiers, such as inorganic substances, were also significantly involved in the emulsions’ destabilization. Finally, the emulsion consisting of 0.5% (w/w) LAE-75 and 5% (w/w) soybean oil showed considerable stability during storage up to 30 days at different temperatures (5 or 25 °C). Therefore, Limnophila aromatica extract has a potential application as a new source of natural emulsifier. Full article

We discuss the peculiarities of the structure of the interface between a metal and a stable colloidal dispersion of charged nanoparticles in an electrolyte. It is demonstrated that a quasi-2D ionic structure of elevated density arises in its vicinity due to the effect of electrostatic image forces. The stabilized colloidal particles, being electroneutral and spatially distributed objects in the bulk of the electrolyte and approaching the interface, are attracted to it. In their turn, the counterions forming their coat partially retract into the 2D-layer, which results in an acquisition by the colloidal particle of the effective charge $e{Z}^{*}\gg e$ and which, together with its mirror image, creates the electric dipole. The formed dipoles, possessing the moments directed perpendicularly to the interface, form the gas with repulsion between particles. The intensity of this repulsion, evidently, depends on the value of the effective charge $e{Z}^{*}$ acquired by the nanoparticle having lost a number of counterions. It can be related to the value of the excess osmotic pressure $P_{osm}$ measured in the experiment. On the other hand, this effective charge can be connected by means of the simple geometric consideration with the structural charge $eZ$ of the nanoparticle core being in the bulk of the electrolyte. Full article

We derive the general expression for the diffusiophoretic mobility of a soft particle (i.e., polyelectrolyte-coated hard particle) in a concentration gradient of electrolytes for the case in which the particle’s core size is large enough compared with the Debye length. Therefore, the particle surface can be regarded as planar, and the electrolyte concentration gradient is parallel to the core surface. The obtained expression can be applied for arbitrary values of the fixed charge density of the polyelectrolyte layer and the surface charge density of the particle core. We derive approximate analytic mobility expressions for soft particles of three types, i.e., (i) weakly charged soft particles, (ii) soft particles with a thick polyelectrolyte layer, in which the equilibrium electric potential deep inside the polyelectrolyte layer is equal to the Donnan potential, and (iii) soft particles with an uncharged polymer layer of finite thickness. Full article

Potentiometric titrations have been routinely used to measure the proton-related surface charge density (SCD) of particles in solution. Here, we quantify the SCD of silica nanoparticles (NPs) that are commercially available as charge-stabilized colloids (by the addition of NaOH) in the presence of known amounts of added NaCl. The experimental results are simulated by surface complexation models (SCMs) of the electrical double layer (EDL). The modeling results suggest that involving only the added NaCl electrolyte yields poor agreement between the experiment and the best achievable fit. An increase in the Na concentration accounting for the colloid inherent salt (CIS) associated with these charge-stabilized colloids results in much better simulations. In the available literature, this CIS has often been disregarded. However, in the modeling, the total concentration of Na must be known for a consistent mole balance and derivation of reliable ion-pair binding constants. If the CIS is not accounted for or the original suspensions are not dialyzed, the presence of CIS renders the study of those colloids difficult, particularly when investigating specific ion effects, since the CIS always interferes. In the present work, we show that the SCM-estimated amount of CIS from varying the total salt and solid concentration agrees surprisingly well with the manufacturer specification. Full article

In recent years, the removal of dyes has emerged as a significant problem that attracted several researchers. The search for green and eco-friendly adsorbents has been a never-ending task in environmental protection to overcome this issue. Herein, almond shells (AS) were used as an adsorbent to remove methyl orange (MO) from aqueous solutions. The AS was characterized using several techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR). Adsorption experiments were carried out under different pH, temperature, and AS particle size conditions. Kinetic and isothermal studies revealed that MO adsorption on the AS reached equilibrium at 90 min, following the pseudo-second-order (PSO) kinetic model. The Langmuir adsorption isotherm was found the suitable adsorption model for MO adsorption on AS, showing a maximum adsorption capacity of 15.63 mg/g. Thermodynamic parameters such as the change in standard enthalpy (ΔH°), the change in standard entropy (ΔS°), and the change in standard free energy (ΔG°) indicated that the MO dye adsorption process is non-spontaneous, endothermic, and physical, which was further confirmed from FTIR analysis of AS samples after adsorption. The contaminated sludge was converted into biochar by slow pyrolysis at a temperature of 400 °C for 2 h. Biochar has been exploited for the manufacture of combustible briquettes. Full article

Self-emulsifying microbubbles, especially designed to increase the contrast of ultrasound images by the inclusion of perfluorocarbon molecules, have been studied by thermal analysis techniques. The microbubbles were made of a blend of gas (20%), surfactants (50%) and water (30%). The surfactants were mixtures of polysorbate-85, Span-80, poloxamer 188, glycerol and fluorinated surfactant (Zonyl^®). Microbubbles have been characterized by means of diffusion light scattering and optical imaging. The effect of Zonyl^® on encapsulation rate, as well as gas vaporization temperature and gas release temperature, has been assessed by means of Differential Scanning Calorimetry (DSC) and Thermogravimetric Analyses (TGA). Microscopy and laser granulometry techniques have been also carried out for each formulation in order to determine the number of microbubbles and their size, respectively. Moreover, stability of the emulsions has been evaluated by DSC and confronted with the results obtained from the ultrasound experiments. Average microbubble concentrations of 7.2 × 10⁷ and 8.9 × 10⁷ per mL were obtained for perfluorohexane and perfluoropentane based emulsions, respectively. The present study demonstrates that the amount of encapsulated perfluorocarbon increases and the gas evaporation temperature decreases with the concentration of Zonyl^®. Furthermore, the best ultrasound contrast images have been obtained in vitro with the samples containing the lowest Zonyl^® concentration. An explication regarding the role of Zonyl^® in the emulsion/microbubbles preparations is proposed here in order to optimize self-emulsifying microbubble formulation for pharmaceutical development. Full article

Based on the recent (2015–2021) literature data, the authors analyze the mutual dependence of crystallinity/amorphism and specific surface area and porosity in covalent triazine frameworks (CTFs), taking into account thermodynamic and kinetic control in the synthesis of these 2D nanosheets. CTFs have now become a promising new class of high-performance porous organic materials. They can be recycled and reused easily, and thus have great potential as sustainable materials. For 2D CTFs, numerous examples are given to support the known rule that the structure and properties of any material with a given composition depend on the conditions of its synthesis. The review may be useful for elder students, postgraduate students, engineers and research fellows dealing with chemical synthesis and modern nanotechnologies based on 2D covalent triazine frameworks. Full article

The food industry is trying to reformulate many of its products to replace functional ingredients that are chemically synthesized or isolated from animal sources (such as meat, fish, eggs, or milk) with ingredients derived from plant or microbial sources. This effort is largely a result of the demand for foods that are better for the environment, human health, and animal welfare. Many new kinds of plant- or microbial-derived proteins are being isolated for potential utilization as functional ingredients by the food industry. A major challenge in this area is the lack of standardized methods to measure and compare the functional performance of proteins under conditions they might be used in food applications. This information is required to select the most appropriate protein for each application. In this article, we discuss the physicochemical principles of emulsifier functionality and then present a series of analytical tests that can be used to quantify the ability of proteins to form and stabilize emulsions. These tests include methods for characterizing the effectiveness of the proteins to promote the formation and stability of the small droplets generated during homogenization, as well as their ability to stabilize the droplets against aggregation under different conditions (e.g., pH, ionic composition, temperature, and shearing). This information should be useful to the food industry when it is trying to identify alternative proteins to replace existing emulsifiers in specific food applications. Full article

Immobilization of nanocatalysts on biochar is receiving unprecedented interest among material and catalysis scientists due to its simplicity, versatility, and high efficiency. Herein, we propose a new direct approach to obtain bimetallic copper/nickel nanoparticles loaded on olive stone biochar. The bimetallic-coated biochar and the reference materials, namely bare biochar, copper rich-loaded biochar, and nickel-loaded biochar, were prepared by pyrolysis from olive pit powder particles impregnated first with citric acid (CA) and then with copper and nickel nitrates at 400 °C under nitrogen flow. We employed citric acid in the process in order to examine its effect on the structural and textural properties of biochar supporting the metallic nanoparticles. Surprisingly, citric acid induced the formation of agglomerated or even raspberry-shaped bimetallic copper/nickel nanoparticles. Large 450–500 nm agglomerates of ~80 nm bimetallic CuNi NPs were noted for B-CA@CuNi. Interestingly, for biochar material prepared with initial Cu/Ni = 10 molar ratio (B-CA@CuNi_10/1), the bimetallic NPs formed unusual nanoraspberries (174 ± 8 nm in size), which were agglomerates of individual 10–20 nm CuNi_10/1 nanoparticles. The B-CA@CuNi and reference materials were characterized by Raman spectroscopy, scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and magnetometry. The B-CA@CuNi and B-CA@Ni materials could be efficiently attracted with a magnet but not B-CA@CuNi_10/1 due to the low nickel loading. B-CA@CuNi was tested as a catalyst for the degradation of methyl orange (MO). Discoloration was noted within 10 min, much faster than a similar material prepared in the absence of CA. B-CA@CuNi could be recycled at least 3 times while still exhibiting the same fast catalytic discoloration performance. This paper stresses the important role of citric acid in shaping bimetallic nanoparticles loaded in situ on biochar during the slow pyrolysis process and in enabling faster catalytic discoloration of organic dye solution. Full article

Regenerated fibers can be prepared from a cooled solution of renneted casein micelles in a wet spinning process. For better handling and stability of the fiber, plasticizers, network modifiers or cross-linkers are used in the production process. For that reason, fibers with different glycerol and calcium content are prepared in this study and subsequently treated with the enzyme transglutaminase before being characterized after air drying. In addition to the swelling behavior in NaOH, H₂O, simulated milk ultrafiltrate buffer as well as HCl, the mechanical properties of the fibers are investigated, taking into account their microscopic fine structure. Transglutaminase-treated fibers show sigmoidal absorption curves for all solvents and reach higher equilibrium swelling percentages than untreated fibers. When the calcium content in the coagulation bath is increased from 50 mM to 100 mM, more stabilizing calcium bridges lead to a denser fiber structure that swells more slowly in all solvents considered. With increasing glycerol content, the flexibility of the fibers increases, as indicated by the decrease in elastic moduli, and a fine structure in the sub-µm range becomes visible. The fibers also demonstrate lower elastic moduli when post-treated with transglutaminase. Besides the higher casein content due to the transglutaminase treatment, this could also contribute to the higher equilibrium swelling percentages compared to the untreated fibers. Full article