Colloids Interfaces, Volume 6, Issue 1 (March 2022) – 16 articles

Low charge density nanometric ions were recently shown to bind strongly to neutral hydrated matter in aqueous solution. This phenomenon, called the (super-)chaotropic effect, arises from the partial dehydration of both the nano-ion and the solute, leading to a significant gain in enthalpy. Here, we investigate the chaotropic effect of the polyoxometalate α-PW₁₂O₄₀³⁻ on the triblock copolymer P84: (EO)₁₉(PO)₄₃(EO)₁₉ with (EO)₁₉ the polyethoxylated and (PO)₄₃ the polypropoxylated chains. The combination of phase diagrams, spectroscopic (nuclear magnetic resonance) and scattering (small angle neutron/X-ray scattering) techniques revealed that: (i) below the micellization temperature of P84, PW₁₂O₄₀³⁻ exclusively binds to the propylene oxide moiety of P84 unimers; and (ii) above the micellization temperature, PW₁₂O₄₀³⁻ mostly adsorbs on the ethylene oxide micellar corona. The preferential binding of the PW₁₂O₄₀³⁻ to the PPO chain over the PEO chains suggests that the binding is driven by the chaotropic effect and is reinforced by the hydrophobic effect. At higher temperatures, copolymer micellization leads to the displacement of PW₁₂O₄₀³⁻ from the PPO chain to the PEO chains. This study deepens our understanding of the subtle interplay between the chaotropic and hydrophobic effects in complex salt-organic matter solutions. Full article

Fatty acids, cholesterol, and phospholipids are amphiphilic compounds of biological interest, which form ordered monolayers mimicking biomembranes, and can be studied with the Langmuir technique using surface pressure-area isotherms and compressibility plots. Proteins are also components of biomembranes or are present in body fluids. In this study, the influence of lysozyme on different films of a fatty acid (stearic acid or oleic acid), cholesterol, a phospholipid (dipalmitoylphosphatidylcholine, DPPC, or palmitoyloleoylphosphatidylcholine, POPC), and mixtures of them is presented using a 0.9% saline solution as subphase. Results show that the presence of lysozyme alters the lipid monolayer formation in an important way at the beginning (low surface pressures) and the middle (intermediate surface pressures) parts of the isotherm. At high surface pressures, the phospholipids DPPC and POPC and the saturated fatty acid, stearic acid, expel lysozyme from the surface, while oleic acid and cholesterol permit the presence of lysozyme on it. The mixtures of oleic acid-DPPC also expel lysozyme from the surface at high surface pressures, while mixtures of oleic acid-POPC and cholesterol-POPC permit the presence of lysozyme on it. The compressibility of the monolayer is affected in all cases, with an important reduction in the elastic modulus values and an increase in the fluidity, especially at low and intermediate surface pressures. Full article

Water in oil emulsions have a wide range of applications from chemical technology to microfluidics, where the stability of water droplets is of paramount importance. Here, using an accessible and easily reproducible experimental setup we describe and characterize the dissolution of water in oil, which renders nanoliter-sized droplets unstable, resulting in their shrinkage and disappearance in a time scale of hours. This process has applicability in creating miniature reactors for crystallization. We test multiple oils and their combinations with surfactants exhibiting widely different rates of dissolution. We derived simple analytical equations to determine the product of the diffusion coefficient and the relative saturation density of water in oil from the measured dissolution data. By measuring the moisture content of mineral and silicone oils with Karl Fischer titration before and after saturating them with water, we calculated the diffusion coefficient of water in these two oils. Full article

Video images of ice formation from moist air under temperature and electric potential gradients reveal that ambient electricity enhances ice production rates while changing the habit of ice particles formed under low supersaturation. The crystals formed under an electric field are needles and dendrites instead of the isometric ice particles obtained within a Faraday cage. Both a non-classical mechanism and classical nucleation theory independently explain the observed mutual feedback between ice formation and its electrification. The elongated shapes result from electrostatic repulsion at the crystal surfaces, opposing the attractive intermolecular forces and thus lowering the ice-air interfacial tension. The video images allow for the estimation of ice particle dimensions, weight, and speed within the electric field. Feeding this data on standard equations from electrostatics shows that the ice surface charge density attains 0.62–1.25 × 10⁻⁶ C·m⁻², corresponding to 73–147 kV·m⁻¹ potential gradients, reaching the range measured within thunderstorms. The present findings contribute to a better understanding of natural and industrial processes involving water phase change by acknowledging the presence and effects of the pervasive electric fields in the ambient environment. Full article

Water-in-oil-in-water (W₁/O/W₂) double emulsions must resist W₁–W₁, O–O and W₁–W₂ coalescence to be suitable for applications. This work isolates the stability of the oil droplets in a double emulsion, focusing on the impact of the concentration of the hydrophilic surfactant. The stability against coalescence was measured on droplets ranging in size from millimeters to micrometers, evaluating three different measurement methods. The time between the contact and coalescence of millimeter-sized droplets at a planar interface was compared to the number of coalescence events in a microfluidic emulsion and to the change in the droplet size distributions of micrometer-sized single and double emulsions. For the examined formulations, the same stability trends were found in all three droplet sizes. When the concentration of the hydrophilic surfactant is reduced drastically, lipophilic surfactants can help to increase the oil droplets’ stability against coalescence. This article also provides recommendations as to which purpose each of the model experiments is suited and discusses advantages and limitations compared to previous research carried out directly on double emulsions. Full article

The characteristics of the wetting process of the porous surface of silica gel when penetrated by base liquids (water and n-octane), ethanol and stable drug systems (naproxen, ibuprofen and cyclosporine A), as biologically active substances in two ethanol concentrations, were determined by the wetting rate vs. time. The tests were performed for contacted and non-contacted plates with the vapours of the wetting liquid. Thin-layer liquid chromatography was used to determine the penetration rate of the SiO₂-coated plates, taking into account the linear dependence consistent with the Washburn equation. Additionally, the changes in the adhesive tension ΔG were determined for the tested drugs. Drug stability tests were conducted using the dynamic light scattering technique and microelectrophoresis. The penetration time of the plate depends on the properties and structure of the wetting liquid droplets. The types of interactions (dispersive, electrostatic and hydrogen bonding) formed between the silanol surface groups of the silica gel and the groups contained in the adsorbate particles are also very important factors. The greater the impact force, the slower the wetting process due to the strong penetration of the liquid into the pores of the substrate. The characteristics of the drug wetting/stability process may contribute to the development of their new forms, creating delivery systems with greater efficiency and lower side effects. Full article

New polysaccharides are being intensely studied as sources of edible materials, with potential application in food packaging systems, eco-materials and the pharmaceutical industry. This investigation aimed to develop biopolymer films based on the polysaccharides obtained from chañar (CH) fruit (Geoffrea decorticans). The resulting polysaccharides, from hydrothermal extraction (CHT) and acid extraction (CHA) were hydrodynamically characterized, with density, viscosity, and diffusion coefficient measurements to obtain their properties in an aqueous solution (intrinsic viscosity, shape factor, partial specific volume, hydration value, molecular weight, and hydrodynamic radius). The polysaccharides films (CHTF and CHAF) were characterized with SEM/EDX, DSC, TGA-DTG, FTIR, DRX, mechanical tests, water vapor permeation, colorimetry, antioxidant capacity, and biodegradability, to determine potential applications based on these properties. The results indicated that the extraction method affects the hydrodynamic properties of the obtained polysaccharide. They differ in molecular weight, and R_H of CHT was greater than CHA. Both gums were quasi-spherical, and the ν_a/b value of CHT was more than CHA. The films properties did not present significant differences in most cases. SEM micrographs illustrate that CHAF presents a much rougher surface. The results of the mechanical analysis show that CHTF has better mechanical properties, it has higher elongation at break and tensile strength, with a Young Modulus of 2.8 MPa. Thermal analysis indicates good thermal stability of the films until about 150 °C. The degradation study shows that CH films are biodegradable in a 35 day range. The study of this properties is critical to demonstrate the functionality of biopolymers and their application. The obtained results represent an advantage and evidence that chañar is an interesting source for extract polysaccharides with film forming properties. Full article

Due to the ability of microorganisms to first adhere to a material surface and then to lead to the formation of a biofilm, it is essential to develop surfaces that have antimicrobial properties. It is well known that N-halamine coatings allow us to prevent or minimize such phenomena. In the present work, various polydopamine (PDA) coatings containing chloramine functions were studied. In fact, three PDA-based films were formed by the simple immersion of a gold substrate in a dopamine solution, either at pH 8 in the presence or not of polyethyleneimine (PEI), or at pH 5 in the presence of periodate as an oxidant. These films were characterized by polarization modulation reflection absorption infrared spectroscopy and X-ray photoelectron spectroscopy analyses, and by scanning electron microscopy observations. The chlorination of these PDA films was performed by their immersion in a sodium hypochlorite aqueous solution, in order to immobilize Cl(+I) into the (co)polymers (PDA or PDA–PEI). Finally, antibacterial assays towards the Gram-negative bacteria Escherichia coli (E. coli) and the Gram-positive bacteria Staphylococcus epidermidis (S. epidermidis) were conducted to compare the bactericidal properties of these three N-halamine coatings. Regardless of the bacteria tested, the PDA coating with the best antibacterial properties is the coating obtained using periodate. Full article

Polymers containing magnetic properties play an important role in biomedical therapies, such as embolotherapy or hyperthermia, for their differentiated properties. In this work, magnetite (Fe₃O₄) nanoparticles were synthesized by the coprecipitation method and dispersed into a thermoplastic matrix of poly(vinyl pivalate) through an emulsion polymerization process. The main goal was the individual encapsulation of magnetite nanoparticles to improve the magnetic response of the magneto-polymeric materials using polymerizable carboxylic acids as coating agents, minimizing the leaching of nanoparticles throughout the nanocomposite formation. For this purpose, synthesized magnetite had its surface modified by acrylic acid or methacrylic acid to improve its individual encapsulation during the polymerization step, thus generating a series of magnetic nanocomposite materials containing different amounts of magnetite intended for biomedical applications. X-ray diffractometry and TEM measurements provided a mean size of approximately 8 nm for the pure magnetite nanoparticles and a spherical morphology. Acid-functionalized Fe₃O₄ had a size of approximately 6 nm, while the nanocomposites showed a size of approximately 7 nm. Magnetization measurement provided a saturation magnetization value of approximately 75 emu/g and confirmed superparamagnetic behavior at room temperature. DSC analysis showed a glass transition temperature of 65 °C for poly(vinyl pivalate)-based nanocomposites. The tests realized with homopolymer and magnetic composites against different cell lineages (i.e., fibroblasts, keratinocytes, and human melanoma) to evaluate the levels of cytotoxicity showed good results in the different exposure times and concentrations used, since the obtained results showed cell viability greater than 70% compared to the control group, suggesting that the synthesized materials are very promising for medical applications. Full article

Thin films of chitosan are often deposited on various surfaces to provide them with antiseptic properties. In the presented research, chitosan foils were obtained using two methods and treated with nitrogen plasma. The obtained materials were characterized by measuring the wettability of the test liquids, and the apparent surface free energy was calculated using the Tadmor equilibrium contact angles. The surface topography was characterized using optical profilometry and SEM. On the other hand, the effect of plasma on surface groups was investigated using the FTIR-ATR technique. Plasma activation of the surface increases the polarity of the surface. This is observed in the changed surface roughness and the share of functional groups on the surface. Full article

The micro-scale morphology of the receding contact line of dilute polyethylene oxide solution drops (c ∼ 100 ppm) after impact and inertial spreading on a fluorinated hydrophobic surface is investigated. One can observe the formation of transient liquid filaments and dendritic structures that evolve into a bead-on-a-string structure similar to the well-known capillary breakup mechanism of dilute polymer solutions, which confirm the interaction between stetched polymer coils and the receding three-phase contact line. The estimation of the average polymer force per unit contact line lenght provides a quantitative explanation for the reduction of the contact line retraction velocity reduction observed experimentally. Full article

Catalytic conversion of fructose to levulinic and formic acids over tin-containing superacid (H₀ = −14.52) mixed oxide was studied. Mesoporous ZrO₂–SiO₂–SnO₂ (Zr:Si:Sn = 1:2:0.4) was synthesized by the sol–gel method. The fructose transformation was carried out in a rotated autoclave at 160–190 °C for 1–5 h using a 20 wt.% aqueous solution. The results showed that doping ZrO₂–SiO₂ samples with Sn⁴⁺ ions improved both fructose conversion and selectivity toward levulinic and formic acids. Under optimal conditions of 180 °C, 3.5 h and fructose to catalyst weight ratio 20:1, levulinic and formic acids yields were 80% and 90%, respectively, at complete fructose conversion. At this, humic substances formed in the quantity of 10 wt.% based on the target products. Full article

The microstructure of the aqueous solutions of purified acidic Sophorolipid (SL) has previously been studied using highly sophisticated methods such as SANS and Cryo-TEM. We were interested in whether (a) the main findings also apply to commercially available SL (which is a mixture of acidic and lactonic SL) and (b) more readily available methods such as DLS can be used to gain insight into the molecular aggregation of SL. Our work was motivated by the increasing interest in biosurfactants for applications in personal and household care. Moreover, the origin behind the more or less lack of rheological response to changes in pH is of practical relevance, as it is somewhat unusual for a carboxylate-group containing surfactant. By using DLS microrheology, we could elucidate the aggregation structure and dynamics of the surfactant on a microscopic scale. Surprisingly, the different degrees of protonation only impacted the microscopic properties such as exchange kinetics and the plateau values of the storage moduli. Full article

The colloidal stability of sulfate (SL) and polyimidazolium-modified sulfate (SL-IP-2) latex particles was studied in an ionic liquid (IL) of ethylammonium nitrate (EAN) and its water mixtures. Aggregation rates were found to vary systematically as a function of the IL-to-water ratio. Repulsive electrostatic interactions between particles dominated at low IL concentrations, while they were significantly screened at intermediate IL concentrations, leading to destabilization of the dispersions. When the IL concentration was further increased, the aggregation of latex particles slowed down due to the increased viscosity and finally, a striking stabilization was observed in the IL-rich regime close to the pure IL solvent. The latter stabilization is due to the formation of IL layers at the interface between particles and IL, which induce repulsive oscillatory forces. The presence of the added salt in the system affected differently the structure of the interfaces around SL and SL-IP-2 particles. The sign of the charge and the composition of the particle surfaces were found to be the most important parameters affecting the colloidal stability. The nature of the counterions also plays an important role in the interfacial properties due to their influence on the structure of the IL surface layers. No evidence was observed for the presence of long-range electrostatic interactions between the particles in pure ILs. The results indicate that the presence of even low concentrations of water and salt in the system (as undesirable impurities) can strongly alter the interfacial structure and thus, the aggregation mechanism in particle IL dispersions. Full article

Tailoring conductive polymers with inorganic photocatalysts, which provide photoinduced electron-hole generation, have significantly enhanced composites leading to excellent photoelectrodes. In this work, MnFe₂O₄ nanoparticles prepared by a hydrothermal method were combined with polyaniline to prepare mixed (hybrid) slurries, which were cast onto flexible FTO to prepare photoelectrodes. The resulting photoelectrodes were characterized by XRD, FESEM, HRTEM and UV-VIS. The photoelectrochemical performance was investigated by linear sweep voltammetry and chronoamperometry. The photocurrent achieved by MnFe₂O₄/Polyaniline was 400 μA/cm² at 0.8 V vs. Ag/AgCl in Na₂SO₄ (pH = 2) at 100 mW/cm², while polyaniline alone achieved only 25 μA/cm² under the same conditions. The best MnFe₂O₄/Polyaniline displayed an incident photon-to-current conversion efficiency (IPCE) and applied bias photon-to-current efficiency (ABPE) of 60% at 405 nm wavelength, and 0.17% at 0.8 V vs. Ag/AgCl, respectively. High and stable photoelectrochemical performance was achieved for more than 900 s in an acidic environment. Full article