Il laboratorio "Gocce Schizzinose" mostra ad un pubblico generico alcune proprietà dei materiali, studiate generalmente a livello di scienza di base e con interessanti applicazioni tecnologiche. I partecipanti riescono ad avvicinarsi in maniera intuitiva alla comprensione della chimica-fisica delle superfici e alla reale attività scientifica svolta all'interno di un ente di ricerca, mediante lo svolgimento in prima persona di attività sperimentali. Spesso la figura del ricercatore e l'attività che svolge vengono percepite come distanti dalla realtà e dalla vita quotidiana. Per mezzo di questo laboratorio interattivo, presentato sia a festival scientifici che ad eventi dedicati alle scuole, questa distanza si accorcia e si percepisce un interesse generale dei partecipanti ad approfondire sia gli aspetti legati alla conoscenza scientifica sia quelli più pratici dell'attività di ricerca. Questa vicinanza è resa possibile grazie alla modalità "hands on", per cui il pubblico tocca con mano i concetti scientifici di bagnabilità, modifica di una superficie e tensione superficiale attraverso la realizzazione in prima persona degli esperimenti proposti. Il laboratorio "Gocce Schizzinose" aiuta a comprendere come concetti astratti entrino in gioco in diversi campi legati alla quotidianità, quali la detersione, la cosmesi, l'alimentazione, fino ad arrivare ad applicazioni tecnologiche (es. materiali per l'edilizia, metallurgia, industria navale).

Carbonaceous particles are accounted among the most common environmental pollutants. This makes necessary a careful examination of their potential impact on the physico-chemical properties of different biological films, e.g. tear film, skin, or lung surfactant. This work analyzes the interaction of three different types of carbonaceous particles with Langmuir monolayers of 1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) spread at the water/vapor interface. This type of studies can be exploited as preliminary in vitro tests for evaluating the potential risks and hazards of this type of pollutants for human health, which requires to study the effect of the particles on the ability of lipid layers for reducing the surface tension under static and dynamics conditions. The obtained results have shown that the insertion of particles into lipid films leads to the emergence of excluded area-like effects which modify the interfacial cohesion and packing. This hinders partially the ability of the lipid films for reducing the surface tension, which may present important adverse effects for the normal physiological performance of lipid membranes, and in particular for the performance of lung surfactant layers. Furthermore, the analysis of the response of lipid layers including carbonaceous particles against mechanical stresses also evidenced that particle incorporation worsens the mechanical performance of lipid layers, which may alter both their functional and structural roles.

Pickering emulsions stabilized by the interaction of palmitic acid (PA) and silica nanopar-ticles (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.

The interaction of hydrophobic silicon dioxide particles (fumed silicon dioxide), as model air pollutants, and Langmuir monolayers of a porcine lung surfactant extract has been studied in order to try to shed light on the physicochemical bases underlying the potential adverse effects associated with pollutant inhalation. The surface pressure-area isotherms of lung surfactant (LS) films including increasing amounts of particles revealed that particle incorporation into LS monolayers modifies the organization of the molecules at the water/vapor interface, which alters the mechanical resistance of the interfacial films, hindering the ability of LS layers for reducing the surface tension, and reestablishing the interface upon compression. This influences the normal physiological function of LS as is inferred from the analysis of the response of the Langmuir films upon the incorporation of particles against harmonic changes of the interfacial area (successive compression-expansion cycles). These experiments evidenced that particles alter the relaxation mechanisms of LS films, which may be correlated to a modification of the transport of material within the interface and between the interface and the adjacent fluid during the respiratory cycle.

In this review, we highlight and discuss the effects of interfacial properties on the major mechanisms governing the aging of emulsions: flocculation, coalescence and Ostwald ripening. The process of emulsification is also addressed, as it is well recognized that the adsorption properties of emulsifiers play an important role on it. The consolidated background on these phenomena is briefly summarised based on selected literature, reporting relevant findings and results, and discussing some criticalities. The typical experimental approaches adopted to investigate the above effects are also summarised, underlining in particular the role of adsorption at the droplet interface. Attention is paid to different types of surface-active species involved with emulsion production, including solid particles. The latter being of increasing interest in a wide variety of emulsions-related products and technologies in various fields. The possibility to stop the long term aging caused by Ostwald ripening in emulsions is also discussed, quantifying under which conditions it may occur in practice.

The present work is aimed at investigating the chemicophysical properties of the interface between silicone oils (SOs) used in vitreoretinal surgery and aqueous solutions, in the presence of surfactant biomolecules. Such molecules are thought to play an important role in the formation of SO emulsions in vitrectomised eyes, in which the natural vitreous body has been replaced with a SO. In particular, we have measured the interfacial tension (IT) and the interfacial dilational viscoelasticity (DV) of the interface between SO (Siluron 1000) and serum proteins (albumin and ?-globulins) at various concentrations in a Dulbecco alkaline buffer. The equilibrium IT value is relevant for the onset of emulsification, and the DV influences the stability of an emulsion, once formed. The study is complemented by preliminary emulsification tests. The experimental results show that, when proteins are dissolved in the aqueous solution, the rheological properties of the interface change. The IT decreases significantly for physiological protein concentrations, and the DV modulus achieves high values, even for small protein concentrations. The emulsification tests confirm that, in the presence of proteins, emulsions are stable on the time scale of months. We conclude that the measured values of IT in the presence of serum proteins are compatible with the promotion of droplet formation, which, in addition, are expected to be stable against coalescence. Adsorption of biomolecules at the interface with the SO is, therefore, likely to play an important role in the generation of an emulsion in eyes subjected to vitrectomy. These findings are relevant to identify strategies to avoid or control the formation of emulsions in eyes.

A comparative study is reported on the interfacial properties of a set of surfactants and is discussed in terms of the effects on the features of the corresponding oil-water emulsions. The surfactants are saponin, Tween 80 and citronellol glucoside (CG), while the oil is Miglyol 812N-A Medium Chain Triglyceride (MCT) oil. Due to their high biocompatibility, all these compounds are variously utilized in food, cosmetic or pharmaceutical products. Among the surfactants, which are all soluble in water, CG presents also an important solubility in oil, as shown by the measured partition coefficient. For these systems, dynamic and equilibrium interfacial tensions and dilational viscoelasticity are measured as a function of the surfactant concentration and analyzed according to available adsorption models. In order to compare these results with the time evolution of the corresponding emulsions, the actual surfactant concentration in the matrix phase of the emulsion is accounted for. This may differ significantly from the nominal concentration of the solutions before dispersing them, because of the huge area of droplets available for surfactant adsorption in the emulsion. Using this approach allows the derivation of the correlations between the observed emulsion behavior and the actual surfactant coverage of the droplet interface.

Lipid layers are considered among the first protective barriers of the human body against pollutants, e.g., skin, lung surfactant, or tear film. This makes it necessary to explore the physico-chemical bases underlying the interaction of pollutants and lipid layers. This work evaluates using a pool of surface-sensitive techniques, the impact of carbon black and fumed silica particles on the behavior of Langmuir monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The results show that the incorporation of particles into the lipid monolayers affects the surface pressure-area isotherm of the DPPC, modifying both the phase behavior and the collapse conditions. This is explained considering that particles occupy a part of the area available for lipid organization, which affects the lateral organization of the lipid molecules, and consequently the cohesion interactions within the monolayer. Furthermore, particles incorporation worsens the mechanical performance of lipid layers, which may impact negatively in different processes presenting biological relevance. The modification induced by the particles has been found to be dependent on their specific chemical nature. This work tries to shed light on some of the most fundamental physico-chemical bases governing the interaction of pollutants with lipid layers, which plays an essential role on the design of strategies for preventing the potential health hazards associated with pollution.

An increase in temperature typically leads to a decrease in the interfacial tension of a water/oil interface. The addition of surfactants to the system can complicate the situation significantly, i.e., the interfacial tension can increase or decrease with an increasing temperature. For most concentrations of the two studied surfactants, the cationic tetradecyl trimethyl ammonium bromide (TTAB) and the nonionic tridecyl dimethyl phosphine oxide (C13DMPO), the measured interfacial tension of the aqueous mixed surfactant solutions against hexane increases when the temperature decreases between 30 degrees C and 20 degrees C. However, with a further temperature decrease between 20 degrees C and 15 degrees C, the reverse effect has also been observed at some concentrations, i.e., a decrease of interfacial tension. Additionally, the corresponding dilational interfacial visco-elasticity shows some discrepant temperature effects, depending on the bulk concentration and oscillation frequency. The experiments have been performed with a capillary pressure tensiometer under the conditions of micro-gravity. The reason for the positive and negative interfacial tension and visco-elasticity gradients, respectively, within certain ranges of the temperature, concentration and mixing ratios, are discussed on the basis of all available parameters, such as the solubility and partitioning of the surfactants in the two liquid phases and the oscillation frequency.

In this communication, the single element version of the fractional Maxwell model (single-FMM or Scott-Blair model) is adopted to quantify the observed behavior of the linear interfacial dilational viscoelasticity. This mathematical tool is applied to the results obtained by capillary pressure experiments under low-gravity conditions aboard the International Space Station, for adsorption layers at the hydrocarbon/water interface. Two specific experimental sets of steady-state harmonic oscillations of interfacial area are reported, respectively: a drop of pure water into a Span-80 surfactant/paraffin-oil matrix and a pure n-hexane drop into a C13DMPO/TTAB mixed surfactants/aqueous-solution matrix. The fractional constitutive single-FMM is demonstrated to embrace the standard Maxwell model (MM) and the Lucassen-van-den-Tempel model (L-vdT), as particular cases. The single-FMM adequately fits the Span-80/paraffin-oil observed results, correctly predicting the frequency dependence of the complex viscoelastic modulus and the inherent phase-shift angle. In contrast, the single-FMM appears as a scarcely adequate tool to fit the observed behavior of the mixed-adsorption surfactants for the C13DMPO/TTAB/aqueous solution matrix (despite the single-FMM satisfactorily comparing to the phenomenology of the sole complex viscoelastic modulus). Further speculations are envisaged in order to devise combined FMM as rational guidance to interpret the properties and the interfacial structure of complex mixed surfactant adsorption systems.

In this work we investigate the surface properties and foamability of saponin and mixed saponin-chitosan solutions. These natural compounds are widely used in various cosmetic, pharmaceutical and food technologies because of their efficiency as bio-active components and their biodegradability. These compounds and their mixture were investigated versus the composition by surface tension and dilational rheology measurements and the respective foams analysed at the formation and during their entire time evolution. The results show that these systems present peculiarities relevant for their utilisation as foam stabilisers, such as strong amphiphilicity of saponin and high values of dilational viscoelasticity. The behaviour of foams has been interpreted on the basis of the adsorption properties at liquid-air interface and the interfacial rheology. Specifically, we found a remarkable effect of the chitosan on the long-time stability of foams. This has been explained considering the changes of the bulk properties induced by chitosan, which influence also the dynamics of the saponin adsorption. This work aims to contribute to the development of new formulations of biodegradable and biocompatible foams for industrial applications, where it is advantageous to reduce the use of synthetic surfactants in commercial products.

Diffusing Wave Spectroscopy (DWS) is a technique used to characterize microscopic structure and rheological properties of turbid samples. This is achieved by analyzing the time evolution of coherence speckles of light that has been multiply scattered within the sample. One attractive feature of DWS is that it is non-invasive, and robust. For this reason, DWS has been selected as a diagnostic tool for an experiment module uploaded onboard the International Space Station (ISS) and devoted to the study of soft matter dynamics -related phenomena, among which, the basic mechanisms responsible for emulsions and foams aging. Moreover, the sensitivity of DWS to tiny motions and to fast time scales allows to extend measurements beyond the limits of usual rheological techniques, of micro-imaging and related techniques. However, the accuracy obtainable by DWS measurements is often limited. Here we revise different experimental approaches to the characterization of emulsions by DWS. We provide quantification of the accuracy of the correlation functions and we discuss how this affects the determination of the mechanical moduli, providing an objective criterion to establish the time window over which DWS results are reliable. These concepts are applied to discuss a laboratory prototype and to address the design of the DWS diagnostics suitable for the emulsion studies to be performed onboard the ISS.

We employ Diffusing Wave Spectroscopy (DWS) to characterize microscopic structure, internal dynamics and rheological properties of a paradigmatic emulsion formed by water and dodecane stabilized by the anionic surfactant Sodium Dodecyl Sulfate (SDS). We focus on ageing and stability in the regime of low surfactant concentration, well below the Critical Micellar Concentration (CMC). In the long-time ageing regimes differentiate in stable and unstable, depending on surfactant concentration. For the stable case, ageing affects the dynamics following a power law with an exponent independent on surfactant concentration, presumably related to the late stages of the water drainage process. On the contrary, at constant ageing, the dependence of the dynamics from surfactant concentration shows a slowdown, corresponding to a maximum in the bulk shear mechanical modulus, around [SDS]=2mM which is reminiscent of a similar maximum found by drop tensiometry in the dilational modulus of the single interface. This suggests a consistent picture of the mechanisms (de)stabilizing the emulsion, explained in terms of elementary process at the interface. These results show furthermore that DWS can be a reliable diagnostic for the study of the aging and of the mechanical properties of concentrate emulsions. This might be relevant to control stability of emulsions when a low concentration of surfactant is desired, e.g. for economical or environment reasons.

This work focuses on the surface properties of binary dispersions of nanoparticles, namely Titania (TiO2) and amorphous silica (SiO2), associated to a short chain ionic surfactant (CTAB) which has the role of modifying their amphiphilicity, inducing the segregation of particle-surfactant complexes at the liquid interface. The foams produced by these dispersions are also investigated. The adsorption of these complexes at water-air interfaces has been investigated by surface tension and dilational rheology measurements. The results obtained, discussed on the basis of the main characteristics of the two types of particles, allow us to understand the role of the dispersion composition and, especially, of the cationic surfactant in the determination of the surface activity of the different complexes and of the properties of the mixed NP layers at the water- air interfaces. In particular, important synergetic effects on the interfacial properties have been observed, when both types of particles are adsorbed. These effects reflect in an enhanced stability of the corresponding foams. In addition, the study evidences the possibility to formulate binary dispersions in order to drive selectively the adsorption of one type of particles at the liquid interface, which can be particularly significant for the formulation of particle-stabilized foams with tailored lamella and cell surface composition/structure.

Lung surfactant is a complex mixture of lipids and proteins which plays a major role in the respiratory cycle. This makes necessary to understand the effects of different external factors or agents, for example, inhaled particles, as a potential source of alteration of the normal physiological response of lung surfactant. However, in most cases, in vivo studies are difficult to perform, and preliminary studies based in model systems are required. Films of lipids or mixtures of lipids and proteins at the water-vapor interface are accounted as one of the most useful methodologies for initial assessments of the potential toxicity of inhaled particles. Thus, the study of the modifications induced by the incorporation of colloidal particles in the interfacial properties of layers mimicking some of the physicochemical features of lung surfactant might provide a first evaluation of the risks and hazards associated with the inhalation of particulate matter. Considering the importance of particles in technology and industry, it is mandatory to develop strategies providing information about toxicological aspects of these widespread materials. This review focuses its interest on the recent advancements on the application of studied bases on monolayers at the fluid interface as preliminary assay for deepening on a complex situation with biological interest.

Capillary pressure experiments are performed in microgravity conditions on board the International Space Station to quantify the dynamic interfacial behavior of mixed adsorption layers of TTAB and C13DMPO at the water/hexane interface. While the non-ionic surfactant C13DMPO is soluble in both bulk phases, water and hexane, the cationic surfactant TTAB is only soluble in the aqueous phase. The interfacial layer is thus formed by TTAB molecules adsorbing from the aqueous phase while the C13DMPO molecules adsorb from the aqueous phase, and transfer partially into the hexane phase until both the equilibrium of adsorption and the distribution between the two adjacent liquid phases is established. The experimental constrains as well as all possible influencing parameters, such as interfacial and bulk phase compressibility, interfacial curvature, calibration of pressure and absolute geometry size, are discussed in detail. The experimental results in terms of the dilational interfacial viscoelasticity of the mixed adsorption layers in a wide range of oscillation frequencies show that the existing theoretical background had to be extended in order to consider the effect of transfer of the non-ionic surfactant across the interface, and the curvature of the water/hexane interface. A good qualitative agreement between theory and experiment was obtained, however, for a quantitative comparison, additional accurate information on the adsorption isotherms and diffusion coefficients of the two studied surfactants in water and hexane, alone and in a mixed system, are required.

The control of the behavior of oil in water emulsions requires deeper investigations on the adsorption properties of the emulsion stabilizers at the interfaces, which are fundamental to explain the (de)stabilization mechanisms. In this work, we present an extensive study on oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) below its critical micellar concentration. Dynamic tensiometry, dilational rheology, and electrical conductivity measurements are used to investigate the adsorption properties at the droplet interface, whereas the aging of the respective emulsions was investigated by monitoring the macroscopic thickness of the emulsion layer, by microimaging and dynamic light scattering (DLS) analysis, to get information on the drop size distribution. In addition, the droplet coalescence is investigated by a microscopy setup. The results of this multitechnique study allow deriving a coherent scenario where the adsorption properties of this ionic surfactant relate to those of the emulsion, such as, for example, the prevention of droplet coalescence and the presence of other mechanisms, such as Ostwald ripening, responsible for the emulsion aging.

Abstract.: Particle-laden interfaces are ubiquitous nowadays. The understanding of their properties and structure is essential for solving different problems of technological and industrial relevance; e.g. stabilization of foams, emulsions and thin films. These rely on the response of the interface to mechanical perturbations. The complex mechanical response appearing in particle-laden interfaces requires deepening on the understanding of physico-chemical mechanisms underlying the assembly of particles at interface which plays a central role in the distribution of particles at the interface, and in the complex interfacial dynamics appearing in these systems. Therefore, the study of particle-laden interfaces deserves attention to provide a comprehensive explanation on the complex relaxation mechanisms involved in the stabilization of fluid interfaces. Graphical abstract: [Figure not available: see fulltext.].

Purpose : The formation and stability of emulsions in vitrectomized eyes is linked to the properties of the silicone oil-aqueous humor interface, in particular the surface tension. In the presence of natural surfactants, such as serum and plasma, the value of the surface tension is likely to change, but little quantitative information is presently available. To this end we perform accurate experiments measuring the interfacial properties of silicone oil (Siluron 1000) with anaqueous solution in the presence of endogenous-like proteins that can act as surfactants....

The effect of the incorporation of hydrophilic titanium dioxide (TiO2) nanoparticles on the interfacial properties of Langmuir monolayers of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) has been evaluated combining interfacial thermodynamic studies, dilatational rheology, and Brewster angle microscopy (BAM). The results show that the TiO2 nanoparticles are able to penetrate DPPC layers, modifying the organization of the molecules and, consequently, the phase behavior and viscoelastic properties of the systems. Measurements of dilational viscoelasticity against the frequency have been performed, using the oscillatory barrier method, at different values of the surface pressure corresponding to different degrees of compression of the monolayer. The presence of TiO2 nanoparticles also affects the dynamic response of the monolayer modifying both the quasi-equilibrium dilatational elasticity and the high frequency limit of the viscoelastic modulus. The principal aim of this work is to understand the fundamental physicochemical bases related to the incorporation of specific nanoparticles of technological interest into the interfacial layer with biological relevance such as phospholipid layers. This can provide information on potential adverse effects of nanoparticles for health and the environment.