Surface Properties of Saponin-Chitosan Mixtures.

The surface properties of saponin and saponin-chitosan mixtures were analysed as a function of their bulk mixing ratio using vibrational sum-frequency generation (SFG), surface tensiometry and dilational rheology measurements. Our experiments show that saponin-chitosan mixtures present some remarkable properties, such as a strong amphiphilicity of the saponin and high dilational viscoelasticity. We believe this points to the presence of chitosan in the adsorption layer, despite its complete lack of surface activity. We explain this phenomenon by electrostatic interactions between the saponin as an anionic surfactant and chitosan as a polycation, leading to surface-active saponin-chitosan complexes and aggregates. Analysing the SFG intensity of the O-H stretching bands from interfacial water molecules, we found that in the case of pH 3.4 for a mixture consisting of 0.1 g/L saponin and 0.001 g/L chitosan, the adsorption layer was electrically neutral. This conclusion from SFG spectra is corroborated by results from surface tensiometry showing a significant reduction in surface tension and effects on the dilational surface elasticity strictly at saponin/chitosan ratios, where SFG spectra indicate zero net charge at the air-water interface.

Hydrophobisation of Silica Nanoparticles Using Lauroyl Ethyl Arginate and Chitosan Mixtures to Induce the Foaming Process.

We studied silica suspensions with chitosan and biodegradable synthetic surfactant lauroyl ethyl arginate (LAE). Hydrophilic and negatively charged silica nanoparticles were neutralised due to the coating with chitosan. That presence of LAE led to the partial hydrophobisation of their surface, which favoured their attachment to the surface of a thin foam film. It was found that the presence of small and medium-sized (6-9 nm) hydrophobic particles in the interfacial layer of lamella foam film inhibited the coalescence and coarsening processes, which prolonged the life of the foam. Furthermore, hydrophobising of 30 nm particles allowed the formation of large aggregates precipitating from the mixture under steady-state conditions. These aggregates, however, under the conditions of the dynamic froth flotation process in the foam column, were floated into the foam layer. As a result, they were trapped in the foam film and Plateau borders, effectively preventing liquid leakage out of the foam. These results demonstrate the efficiency of using chitosan-LAE mixtures to remove silica nanoparticles from aqueous phase by foaming and flotation.

Influence of Surfactant Concentration on Spontaneous Emulsification Kinetics.

The kinetics of spontaneous emulsification is investigated on aqueous pendant drops in paraffin oil. Optical microscopy in transmission mode is used for high-spatial-resolution image recording. The influence of a lipophilic surfactant (Span 80) and two water-soluble surfactants (CTAB and SDS) is investigated. As time runs, the drop interface turns opaque due to the formation of microstructures associated with spontaneous emulsification. The time evolution of this phenomenon is shown to depend upon temperature and surfactant concentration, which leads to an overall shrinkage due to gradual water uptake and transport into paraffin oil. Spontaneous emulsification kinetics depends upon the chemical composition. Higher concentrations of Span 80 and CTAB (resp. SDS) are shown to promote (resp. hinder) water transport. This work provides new insights into the understanding of spontaneous emulsification when combining the properties of non-ionic and ionic surfactants.

A Multistate Adsorption Model for the Characterization of C13DMPO Adsorption Layers at the Aqueous Solution/Air Interface.

Experimental data for tridecyl dimethyl phosphine oxide (C13DMPO) adsorption layers at the water/air interface, including equilibrium surface tension and surface dilational viscoelasticity, are measured by bubble and drop profile analysis tensiometry at different solution concentrations and surface area oscillation frequencies. The results are used to assess the applicability of a multistate model with more than two possible adsorption states. For the experiments with single drops, the depletion of surfactant molecules due to adsorption at the drop surface is taken into account. For the assessment, the same set of model parameters is used for the description of all obtained experimental dependencies. The agreement between the proposed model and the experimental data shows that for the nonionic surfactant C13DMPO, the description of the adsorption layer behavior by three adsorption states is superior to that with only two adsorption states.

Evaluating the Impact of Hydrophobic Silicon Dioxide in the Interfacial Properties of Lung Surfactant Films.

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.

Biocompatibility of intraocular liquid tamponade agents: an update.

Intraocular liquids tamponade agents, such as perfluorocarbon liquids (PFCLs), semifluorinated alkanes (SFAs), silicone oils (SOs) and heavy silicone oils (HSOs), are a crucial intraoperative and/or postoperative tool in vitreoretinal surgery, in particular for the management of complex vitreoretinal diseases. However, their use is not without complications, which are potentially severe. Consequently, a growing interest has been devoted to the biocompatibility of these compounds and the adequacy of current regulations that should guarantee their safety. Obviously, an updated knowledge on research findings and potential risks associated to the use of intraocular liquid compounds is essential, not only for vitreoretinal surgeons, but also for any ophthalmologist involved in the management of patients receiving intraocular liquid tamponades. In light of this, the review provides a comprehensive characterisation of intraocular liquid tamponades, in terms of physical and chemical properties, current clinical use and possible complications. Moreover, this review focuses on the safety profile of these compounds, summarising the existing regulation and the available evidence on their biocompatibility.

Emulsification and emulsion stability: The role of the interfacial properties.

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.

Recent developments in emulsion characterization: Diffusing Wave Spectroscopy beyond average values.

We report here an overview of current trends and a selection of recent results regarding the characterization of emulsions by Diffusing Wave Spectroscopy (DWS). We provide a synopsis of the state of the art of the DWS technique, and a critical discussion of experiments performed on samples in which Brownian and ballistic dynamics coexist. A novel analysis scheme is introduced for DWS experiments on creaming or sedimenting emulsions, allowing to extract not only average values for drop size and drop dynamics - as usual in DWS - but also properties related to the width of the distributions governing these quantities. This analysis scheme starts from a realistic Monte Carlo simulation of light diffusing in the volume of the sample and reaching the detector. This simulation is more accurate than the analytical expressions available for the idealized geometries normally used in DWS interpretation. By disentangling Brownian and ballistic motions we directly access the variance of velocity distribution, σv. In relatively unstable emulsions σv governs the frequency of drop-drop collisions and subsequent coalescence events. Furthermore, when gravity dominates dynamics, as in emulsions subject to sedimentation or creaming, σv is strongly related to the 2nd and 4th moments of drop size distribution. This novel analysis scheme is exemplified investigating freshly formed model emulsions. Results are validated by comparison with microscopy imaging. This analysis is then extended to emulsions with a much broader drop size distribution, resembling those that are planned to be investigated in microgravity by the Soft Matter Dynamics facility onboard the International Space Station (ISS). This review is concluded by sketching some promising directions, and suggesting useful complementarities between DWS and other techniques, for the characterization of transient regimes in emulsions, and of destabilization processes of great practical importance.

The Role of Endogenous Proteins on the Emulsification of Silicone Oils Used in Vitreoretinal Surgery.

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 γ-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.

Surface properties and foamability of saponin and saponin-chitosan 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.

Adsorption of Sodium Dodecyl Sulfate at Water-Dodecane Interface in Relation to the Oil in Water Emulsion Properties.

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.

Effect of the Incorporation of Nanosized Titanium Dioxide on the Interfacial Properties of 1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine Langmuir Monolayers.

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.

Hydrophobic Silica Nanoparticles Induce Gel Phases in Phospholipid Monolayers.

Silica nanoparticles (SiNP) can be incorporated in phospholipid layers to form hybrid organic-inorganic bidimensional mesostructures. Controlling the dynamics in these mesostructures paves the way to high-performance drug-delivery systems. Depending on the different hydrophobicity/hydrophilicity of SiNP, recent X-ray reflectivity experiments have demonstrated opposite structural effects. While these are reasonably well understood, less is known about the effects on the dynamics, which in turn determine molecular diffusivity and the possibility of drug release. In this work we characterize the dynamics of a mixed Langmuir layer made of phospholipid and hydrophobic SiNP. We combine X-ray photon correlation spectroscopy and epifluorescence discrete Fourier microscopy to cover more than 2 decades of Q-range (0.3-80 µm(-1)). We obtain evidence for the onset of an arrested state characterized by intermittent stress-relaxation rearrangement events, corresponding to a gel dominated by attractive interactions. We compare this with our previous results from phospholipid/hydrophilic SiNP films, which show an arrested glassy phase of repulsive disks.

2D dynamical arrest transition in a mixed nanoparticle-phospholipid layer studied in real and momentum spaces.

We investigate the interfacial dynamics of a 2D self-organized mixed layer made of silica nanoparticles interacting with phospholipid (DPPC) monolayers at the air/water interface. This system has biological relevance, allowing investigation of toxicological effects of nanoparticles on model membranes and lung surfactants. It might also provide bio-inspired technological solutions, exploiting the self-organization of DPPC to produce a non-trivial 2D structuration of nanoparticles. The characterization of interfacial dynamics yields information on the effects of NPs on the mechanical properties, important to improve performances of systems such as colloidosomes, foams, creams. For this, we combine micro-tracking in real-space with measurement in momentum-space via x-ray photon-correlation spectroscopy and Digital Fourier Microscopy. Using these complementary techniques, we extend the spatial range of investigation beyond the limits of each one. We find a dynamical transition from Brownian diffusion to an arrested state driven by compression, characterized by intermittent rearrangements, compatible with a repulsive glass phase. The rearrangement and relaxation of the monolayer structure results dramatically hindered by the presence of NPs, which is relevant to explain some the mechanical features observed for the dynamic surface pressure response of these systems and which can be relevant for the respiratory physiology and for future drug-delivery composite systems.

Effect of silica nanoparticles on the interfacial properties of a canonical lipid mixture.

The incorporation of silica nanoparticles (NPs) from the subphase into Langmuir lipid monolayers formed by three components, 1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC), 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) and Cholesterol (Chol), modifies the thermodynamic and rheological behavior, as well as the structure of the pristine lipid film. Thus, the combination of structural characterization techniques, such as Brewster Angle Microscopy (BAM) and Atomic Force Microscopy (AFM), with interfacial thermodynamic and dilational rheology studies has allowed us to deepen on the physico-chemical bases governing the interaction between lipid molecules and NPs. The penetration of NPs driven by the interaction (electrostatic or hydrogen bonds) with the polar groups of the lipid molecules affects the phase behaviour (surface pressure-area, П-A , isotherm) of the monolayer. This can be easily rationalized considering the modification of the packing and cohesion of the molecules at the interface as revealed BAM and AFM images. Furthermore, oscillatory barrier experiments have allowed obtaining information related to the effect of NPs on the monolayer response under dynamic conditions that presents a critical impact on the characterization of biological relevant systems because most of the processes of interest for these systems present a dynamic character.

Carbon Soot-Ionic Surfactant Mixed Layers at Water/Air Interfaces.

An experimental study is here presented on the properties of aqueous dispersions containing carbon nanoparticles and different ionic surfactants which can modify the degree of hydrophobicity/philicity of particles favoring their transfer from the dispersion bulk to the interfacial layer. Aim of this work is to understand the particle-surfactant and particle-fluid interface interactions and their effect on those macroscopic surface properties of the mixed systems which are expected related to the stability and structure of the respective particle stabilized foams. To this purpose a systematic characterization of dispersions have been carried out, based on surface tension measurement against the surfactant concentration, using a drop Profile Analysis Tensiometer (PAT). These results have been crossed with the characterization of the bulk dispersion by Dynamic Light Scattering (DLS) and ζ-potential measurements to check the effects of surfactant on the particle aggregation and on the particle surface charge, respectively. The stability of the foams obtained with the same compositions has been also investigated and correlated to the other surface and bulk properties.

Surfactant induced complex formation and their effects on the interfacial properties of seawater.

The effect of a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), on the interfacial properties of seawater has been studied by dynamic and equilibrium surface tension and by dilational rheology essays. Important modifications of the surface tension and dilational rheology response have been observed already at the very low CTAB concentrations, where the effects due to the high ionic strength are negligible. The comparison with the effects of CTAB in different seawater models, or in natural seawater fractions, points out the establishment of strong interactions between the surfactant molecules and the lipophilic fraction of organic material dispersed/dissolved in seawater, affecting the interfacial activity of the molecules. Considering the biochemical richness of seawater, these results can be explained assuming interaction mechanisms and adsorption schemes similar to those speculated for protein and other macromolecules in the presence of surfactants, which in fact show similar features. Thus already at the low concentrations the surfactant molecules form highly surface-active complexes with part of the organic fraction of seawater. At the larger surfactant concentrations these complexes compete for adsorption with an excess of free CTAB molecules which, according to the thermodynamic conditions, are most favoured to occupy the liquid interface. The results of this study underline the important role of the sea organic content in enhancing the surface-activity of surfactants, which is relevant for a deeper understand of the direct and indirect effects of these types of pollutants on the physico-chemical environment in the sea coastal areas and develop mitigation strategies.

Two-dimensional DPPC based emulsion-like structures stabilized by silica nanoparticles.

We studied the mechanical and structural properties of mixed surface layers composed by 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and silica nanoparticles (NPs). These layers are obtained by spreading a DPPC Langmuir monolayer on a colloidal silica dispersion. The transfer/incorporation of NPs into the DPPC monolayer, driven by electrostatic interactions, alters the molecular orientation, the mechanisms of domain formation, and consequently the phase behavior of the surface layer during compression. The investigation of these systems by means of complementary techniques (Langmuir trough, fluorescence microscopy, ellipsometry, and scanning electron microscopy (SEM)) shows that the incorporated NPs preferentially distribute along the liquid expanded phase of DPPC. The layer assumes the stable and homogeneous bidimensional structure of a two-dimensional (2D) analogue of a Pickering emulsion. In fact, the presence of particles provides a circular shape to the DPPC domains and stabilizes them against growth and coalescence during the monolayer compression.

Effect of tea polyphenols on the dilational rheology of human whole saliva (HWS): Part 1, HWS characterization.

Human whole saliva (HWS) is a physiological secretion that performs a number of essential functions including protection of oral health, lubrication of mouth tissues and food pre-digestion. The complexity of the saliva proteome reflects the unique physiochemical functionality of this biofluid. In addition, saliva influences the transduction of aroma, taste and tactile (mouthfeel) perceptions through the interaction with food and beverages. This work, which is presented as two distinct contributions, reports on the extensive interfacial properties characterization (air-liquid) of saliva either alone or after exposure to tea polyphenols. This first part discusses the complex nature of the salivary film in terms of kinetic and viscoelastic (dilational surface rheology) properties. The formation of the surface film is analyzed with time and explained in terms of the progressively irreversible adsorption of protein fractions of larger molecular weight. The viscoelastic response to appropriate frequency modulation is modelled using a general mixed kinetic model, which satisfactorily reproduces the experimental data in better agreement than the traditional Lucassen diffusive model.