Colloids and Interfaces

The concepts hybrid and hybridization are common in many scientific fields, as in the taxonomic parts of botany and zoology, in modern genetic, and in the quantum–mechanical theory of atomic–molecular orbitals, which are of foremost relevance in most aspects of modern chemistry. Years later, scientists applied the concept hybrid to colloids, if the particles’ domains are endowed with functionalities differing each from the other in nature and/or composition. For such denomination to be fully valid, the domains belonging to a given hybrid must be recognizable each from another in terms of some intrinsic features. Thus, the concept applies to particles where a given domain has its own physical state, functionality, or composition. Literature examples in this regard are many. Different domains that are present in hybrid colloids self-organize, self-sustain, and self-help, according to the constraints dictated by kinetic and/or thermodynamic stability rules. Covalent, or non-covalent, bonds ensure the formation of such entities, retaining the properties of a given family, in addition to those of the other, and, sometimes, new ones. The real meaning of this behavior is the same as in zoology; mules are pertinent examples, since they retain some features of their own parents (i.e., horses and donkeys) but also exhibit completely new ones, such as the loss of fertility. In colloid sciences, the concept hybrid refers to composites with cores of a given chemical type and surfaces covered by moieties differing in nature, or physical state. This is the result of a mimicry resembling the ones met in a lot of biological systems and foods, too. Many combinations may occur. Silica nanoparticles on which polymers/biopolymers are surface-bound (irrespective of whether binding is covalent or not) are pertinent examples. Here, efforts are made to render clear the concept, which is at the basis of many applications in the biomedical field, and not only. After a historical background and on some features of the species taking part to the formation of hybrids, we report on selected cases met in modern formulations of mixed, and sometimes multifunctional, colloid entities. Full article

Biological membrane is composed of lipid molecules, because of its fluidity, it is possible to carry out physiological functions. Therefore, it is important to study the hydrodynamic properties of membranes toward understanding its function. Here, we observed the dynamical behavior of a lipid monolayer on the water surface under Marangoni flow. By using X-ray reflectometry, we obtained the tilt angle of the hydrocarbon chains of the lipid at different surface pressures. Comparing them with the dynamical surface pressure under Marangoni flow, it was found that the lipid molecules in rotational rather than translational motion. At low surface pressure, the molecular tilt angle is reduced by 20 degrees, even though the molecular area is reduced by at most 10%. Full article

Langmuir monolayers containing different amounts of cholesterol and cholesteryl stearate were studied at two different temperatures (24 °C and 35 °C). The main goal was to contribute towards the understanding of how the variations in the chemical composition may affect the physico-chemical properties of these specific lipid monolayers. The model mixture was chosen considering that cholesteryl esters are present in cell membranes and some other biological systems, including human tear lipids. Therefore, an investigation into the effect of the lipid monolayer composition on their interfacial properties may elucidate some of the fundamental reasons for the deficiencies in cell membranes and tear film functioning in vivo. The experimental results have shown that the molar ratio of the mixture plays a crucial role in the modulation of the Langmuir film properties. The condensing effects of the cholesterol and the interactions between the lipids in the monolayer were the main factors altering the monolayer response to dilatational deformation. The modification of the mixture compositions leads to significant changes in the Langmuir films and the mechanical performance, altering the ability of the monolayer to reduce the surface tension and the viscoelastic properties of the monolayers. This suggests that subtle modifications of the biomembrane composition may significantly alter its physiological function. Full article

Confinement can induce substantial changes in the physical properties of macromolecules in suspension. Soft confinement is a particular class of restriction where the boundaries that constraint the particles in a region of the space are not well-defined. This scenario leads to a broader structural and dynamical behavior than observed in systems enclosed between rigid walls. In this contribution, we study the ordering and diffusive properties of a two-dimensional colloidal model system subjected to a one-dimensional parabolic trap. Increasing the trap strength makes it possible to go through weak to strong confinement, allowing a dimensional transition from two- to one-dimension. The non-monotonic response of the static and dynamical properties to the gradual dimensionality change affects the system phase behavior. We find that the particle dynamics are connected to the structural transitions induced by the parabolic trap. In particular, at low and intermediate confinement regimes, complex structural and dynamical scenarios arise, where the softness of the external potential induces melting and freezing, resulting in faster and slower particle diffusion, respectively. Besides, at strong confinements, colloids move basically along one direction, and the whole system behaves structurally and dynamically similar to a one-dimensional colloidal system. Full article

The scientific relevance of quinolines is strictly linked to the fine-tuning of their features by functionalizing the heterocyclic core. Consequently, the compounds of this class are very versatile and can be used as possible drugs for a lot of medical applications. In this work, the inclusion of eight synthetic quinoline derivatives in liposomes formulated with different lipids was investigated in terms of the encapsulation efficiency and to highlight the effect on the liposome size distribution and thermotropic behavior. Excellent encapsulation was accomplished with all the quinoline/phospholipid combinations. Differences in the interactions at the molecular level, dependent on the quinoline molecular scaffolds and lipid structure, were observed, which could significantly bias the interaction with the drug and its release in pharmaceutical applications. Experiments in combination with computational studies demonstrated that the UV absorption of quinolines with expanded conjugation could be affected by the environment polarity. This was probably due to a solvent-dependent ability of these quinolines to stack into aggregates, which could also occur upon inclusion into the lipid bilayer. Full article

Adsorption of myoglobin molecules at negatively charged polystyrene microparticles was studied using the dynamic light scattering (DLS), electrophoresis (LDV) and the solution depletion method involving atomic force microscopy (AFM). The measurements were carried out at pH 3.5 and NaCl concentration of 10⁻² and 0.15 M. Initially, the stability of myoglobin solutions and the particle suspensions as a function of pH were determined. Afterward, the formation of myoglobin molecule corona was investigated via the direct electrophoretic mobility measurements, which were converted to the zeta potential. The experimental results were quantitatively interpreted in terms of the general electrokinetic model. This approach yielded the myoglobin corona coverage under in situ conditions. The maximum hard corona coverage was determined using the AFM concentration depletion method. It was equal to 0.9 mg m⁻² for the NaCl concentration in the range 0.01 to 0.15 M and pH 3.5. The electrokinetic properties of the corona were investigated using the electrophoretic mobility measurements for a broad pH range. The obtained results confirmed that thorough physicochemical characteristics of myoglobin molecules can be acquired using nM amounts of the protein. It was also argued that this method can be used for performing electrokinetic characteristics of other proteins such as the SARS-Cov-2 spike protein exhibiting, analogously to myoglobin, a positive charge at acidic pHs. Full article

Positively charged water-solid interfaces are prepared by adsorption of a cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) from aqueous solutions to planar silica substrates. These substrates are characterized by atomic force microscopy (AFM), optical reflectivity, and streaming current measurements. By tuning the amount of adsorbed polyelectrolyte, the surface charge of the substrate can be systematically varied. These substrates are further used to study deposition of sulfate latex nanoparticles, which is also accomplished by optical reflectivity. This deposition process is found to be consistent with an extension of the random sequential adsorption (RSA) model in a semi-quantitative fashion. Such deposition studies were further used to ascertain that the substrates obtained by in situ and ex situ functionalization behave in an identical fashion. Full article

During the past 30 years, more and more 3D-printing techniques based on suspensions with specific rheological properties have been innovated and improved. In this review, principles of dispersing and controlling powders for suspension-based 3D printing are summarized. The suspensions for direct ink writing (DIW) are taken as an example for 3D printing. According to the rheological property requirement of suspensions for direct ink writing, the routes on how its rheological properties can be manipulated are summarized and classified into two categories: I. self-solidification route; II. assistant-solidification route. The perspective on the future of 3D-printing techniques based on suspensions is also discussed. Full article

In this paper, we present the unsteady translational motion of a porous spherical particle in an incompressible viscous fluid. In this case, the modified Navier–Stokes equation with fractional order time derivative is used for conservation of momentum external to the particle whereas modified Brinkman equation with fractional order time derivative is used internal to the particle to govern the fluid flow. Stress jump condition for the tangential stress along with continuity of normal stress and continuity of velocity vectors is used at the porous–liquid interface. The integral Laplace transform technique is employed to solve the governing equations in fluid and porous regions. Numerical inversion code in MATLAB is used to obtain the solution of the problem in the physical domain. Drag force experienced by the particle is obtained. The numerical results have been discussed with the aid of graphs for some specific flows, namely damping oscillation, sine oscillation and sudden motion. Our result shows a significant contribution of the jump coefficient and the fractional order parameter to the drag force. Full article

An oscillating drop rheometer capable of operating under conditions of high pressure and high temperature has been built. The oscillating drop mechanism was able to support pressures as high as 1300 bar and successfully performed oscillations at constant pressure. Apparent elastic and viscous complex moduli were measured for a system of CO₂ and synthetic seawater containing 100 ppm of a linear alkyl ethoxylate surfactant for different pressures and temperatures. The moduli had strong dependencies on both pressure and temperature. At temperatures of 40 and 80 °C, the apparent elastic modulus passed through a maximum for pressures between 100 and 300 bar. The harmonic distortion of the oscillations was calculated for all measurements, and it was found that drop oscillations below ca. 2.6 µL caused distortions above 10% due to a mechanical backlash of the motor. Full article

Driven transport of dilute polymer solutions through porous media has been simulated using a recently proposed novel dissipative particle dynamics method satisfying the no-penetration and no-slip boundary conditions. The porous media is an array of overlapping spherical cavities arranged in a simple cubic lattice. Simulations were performed for linear, ring, and star polymers with 12 arms for two cases with the external force acting on (I) both polymer and solvent beads to model a pressure-driven flow; (II) polymer beads only, similar to electrophoresis. When the external force is in the direction of a principal axis, the extent of change in the polymers’ conformation and their alignment with the driving force is more significant for case I. These effects are most pronounced for linear chains, followed by rings and stars at the same molecular weight. Moreover, the polymer mean velocity is affected by its molecular weight and architecture as well as the direction and strength of the imposed force. Full article

Double emulsions are a promising formulation for encapsulation and targeted release in pharmaceutics, cosmetics and food. An inner water phase is dispersed in an oil phase, which is again emulsified in a second water phase. The encapsulated inner water phase can be released via diffusion or via coalescence, neither of which is desired during storage but might be intended during application. The two interfaces in a double emulsion are stabilized by a hydrophilic and a lipophilic surfactant, to prevent the coalescence of the outer and the inner emulsion, respectively. This study focuses on the influence of the hydrophilic surfactant on the release of inner water or actives encapsulated therein via coalescence of the inner water droplet with the outer O–W2 interface. Since coalescence and diffusion are difficult to distinguish in double emulsions, single-droplet experiments were used to quantify differences in the stability of inner droplets. Different lipophilic (PGPH and PEG-30 dipolyhydroxylstearate) and hydrophilic surfactants (ethoxylates, SDS and polymeric) were used and resulted in huge differences in stability. A drastic decrease in stability was found for some combinations, while other combinations resulted in inner droplets that could withstand coalescence longer. The destabilization effect of some hydrophilic surfactants depended on their concentration, but was still present at very low concentrations. A huge spread of the coalescence time for multiple determinations was observed for all formulations and the necessary statistical analysis is discussed in this work. The measured stabilities of single droplets are in good accordance with the stability of double emulsions for similar surfactant combinations found in literature. Therefore, single droplet experiments are suggested for a fast evaluation of potentially suitable surfactant combinations for future studies on double-emulsion stability. Full article

We demonstrate a method for the formation of multilayers composed of reduced graphene oxide (rGO), which can be used for transparent, conducting thin films. Using the layer-by-layer (LbL) assembly of positively and negatively charged GO sheets, we could obtain thin films with highly controllable sheet resistance. The natural negative charge of graphene oxide was turned to positive by the amidation reaction. After forming the multilayer films, the graphene oxide underwent thermal reduction at temperatures above 150 °C. The (rGO⁺/rGO⁻) films were characterized by UV-Vis and scanning electron microscopy (SEM), and their conductivity was measured by the four-point method. We found that after deposition of five (rGO⁺/rGO⁻), the coating structure reached the percolation limit, and the film resistance decreased more gradually to around 20 kΩ/sq for the films obtained by eleven deposition cycles with graphene oxide reduced at 250 °C. The formation of thin films on polyimide allows the forming of new flexible conductive materials, which can find applications, e.g., in biomedicine as new electroactive, low-cost, disposable sensors. Full article

An analytical study of the electroosmosis and electric conduction of electrolyte solutions in a fibrous medium composed of parallel charge-regulating cylinders with arbitrary electric double layer thickness is presented. A linearized charge regulation model was adopted for the association and dissociation reactions occurring at the amphoteric functional groups over the surfaces of the cylinders, and a unit cell model was employed to accommodate interactions among the cylinders. The electrokinetic equations governing the ionic concentration, electric potential, and liquid flow fields were solved at low zeta potential for the cylinders. Explicit formulas for the electroosmotic mobility and effective electric conductivity in the fiber matrix were obtained. The results indicate that the charge regulation characteristics, such as the equilibrium constants of the reactions occurring at the cylinders’ surfaces and the bulk concentration of the charge-determining ions, influence the surface charge density and potential, electroosmotic mobility, and effective electric conductivity substantially. Full article

The stratum corneum, the most superficial layer of the skin, protects the body against environmental hazards and presents a highly selective barrier for the passage of drugs and cosmetic products deeper into the skin and across the skin. Nanomaterials can effectively increase the permeation of active molecules across the stratum corneum and enable their penetration into deeper skin layers, often by interacting with the skin and creating the distinct sites with elevated local concentration, acting as reservoirs. The flux of the molecules from these reservoirs can be either limited to the underlying skin layers (for topical drug and cosmeceutical delivery) or extended across all the sublayers of the epidermis to the blood vessels of the dermis (for transdermal delivery). The type of the nanocarrier and the physicochemical nature of the active substance are among the factors that determine the final skin permeation pattern and the stability of the penetrant in the cutaneous environment. The most widely employed types of nanomaterials for dermal and transdermal applications include solid lipid nanoparticles, nanovesicular carriers, microemulsions, nanoemulsions, and polymeric nanoparticles. The recent advances in the area of nanomaterial-assisted dermal and transdermal delivery are highlighted in this review. Full article

The increasing popularity of flow field-based data analysis (FFBDA) techniques has a paradigmatic example in the routines already developed for the rotational oscillating bicone bob interfacial shear rheometer. Such routines use a second order centered finite difference (SOCFD) discretization scheme, in both the vertical and radial coordinates, for the velocity field in the bulk fluid subphase and a first order forward finite difference (FOFFD) scheme in the vertical coordinate for the velocity field at the air/water interface. Such a mixture of schemes causes non-smooth flow fields at the interface that can be tackled by appropriately devising a SOCFD scheme for the vertical coordinate at the interface using a line of “phantom” nodes that merely serve to adequately merge the Navier–Stokes equations and the Boussinesq–Scriven boundary condition at the interface. Here we report on a detailed analysis of the quantitative improvements of such a scheme over the previous one by comparing the structure of the flow fields at and close to the interface, the differences in the interfacial and bulk drag torques on the bicone bob, and the differences in the torque/displacement complex amplitude ratio. Full article

The adsorption behaviour of linear poly(oxyethylene) alkyl ether (C_nEO_m) is best described by a reorientation model. Based on a complete set of experimental data, including the adsorption kinetics, the equilibrium surface tension isotherm and the surface dilational visco-elasticity, the thermodynamic and kinetic adsorption parameters for some C_nEO_m at the water/air interface were determined. For the study, six C_nEO_m surfactants were selected (n = 10, 12 and 14 and m = 4, 5 and 8) and were studied by bubble profile analysis and maximum bubble pressure tensiometry. A refined theoretical model based on a reorientation-adsorption model combined with a diffusion-controlled adsorption kinetics and exchange of matter allowed us to calculate the surface layer composition by adsorbing molecules in different orientations. It turns out that at larger surface coverage, the adsorption rate decreases, i.e., the apparent diffusion coefficients are smaller. This deceleration can be explained by the transition of molecules adsorbed in a state of larger molar surface area into a state with smaller molar surface area. Full article

Nanocomposite inks composed of nickel–silver core–shell and silver nanoparticles (NPs) can combine the advantages of lower cost, high conductivity, and low-temperature sintering processes, which have attracted much attention in the development of materials for printed flexible electronics. In this context, in the present paper, we report the process of preparation of nanocomposite ink containing nickel–silver core–shell nanoparticles, as the main filler, and silver nanoparticles, as doping material, and their application for the fabrication of conductive coatings. It was found that the addition of a low concentration of Ag NPs to ink formulation based mainly on low-cost Ni-Ag NPs improves the conductive properties of coatings fabricated by ink deposition on a glass substrate. Two types of prepared nanocomposite ink coatings showed promising properties for future application: (1) doped with 0.5% of Ag NPs sintered at 200 °C as low cost for larger industrial application and, (2) containing 1% of Ag NPs sintered at 150 °C for the fabrication of conductive printed patterns on flexible substrates. The conductivity of such nanocomposite films was similar, about of 6 × 10⁶ S/m, which corresponds to 35% of that for a bulk nickel. Full article