Surfactant Film Research Articles

Formation of Concentric Silica Nanogrooves Guided by the Curved Surface of Silica Particles

The flexible control of nanopatterns by a bottom-up process at the nanometer scale is essential for nanofabrication with a finer pitch. We have previously reported that for the fabrication of linear nanopatterns with sub-5 nm periodicity on Si substrates the outermost surfaces of assembled micelles facing the substrates can be replicated with soluble silicate species generated from the Si substrates under basic conditions. In this study, concentrically arranged nanogrooves with a sub-5 nm periodicity were prepared on Si substrates by replicating the outermost surfaces of bent micelles guided by silica particles. The Si substrates, where silica particles and surfactants films were deposited, were exposed to an NH3-water vapor mixture. During the vapor treatment, cylindrical micelles became arranged in concentric patterns centered on the silica particles, and their outermost surfaces facing the substrates were replicated by soluble silicate species on the Si substrates. The thinness of the surfactant film on the substrate is crucial for the formation of concentric silica nanogrooves because the out-of-plane orientations of the micelles are suppressed at the interface. Surprisingly, the domains of the concentric silica nanogrooves spread to much larger areas than the maximum cross-sectional areas of the particles, and the size of the domains increased linearly with the radii of the particles. The extension of concentric nanogrooves is discussed on the basis of the orientational elastic energies of the micelles around one silica particle. This study of the formation of bent nanogrooves guided by the outlines of readily deposited nanoscale objects provides a new nanostructure-guiding process.

Structural evolution in metallomicroemulsions - the effect of increasing alcohol hydrophobicity.

Small-angle neutron scattering and contrast variation has been employed to quantify how a series of alcohols with increasing hydrophobicity exert different abilities to structure a model toluene based metallomicroemulsion - a microemulsion system stabilised with a metallosurfactant. Classical microemulsion phase evolution and droplet structure are observed, leading to an oil rich core stabilised by a surfactant film containing a highly concentrated, hydrated metal ion layer.

Improved effect of deep eutectic solvents on polymeric film of surfactant: application in determination and discrimination of dihydroxybenzene isomers as model molecules

The simultaneous determination of hydroquinone and catechol with different deep eutectic solvents (DESs) employed in the polymerization step of cetyltrimethylammonium bromide (CTAB) on an oxidized glassy carbon electrode is studied.

Effects of magnetic fields on capillary-gravity waves in the presence of magnetic surfactants

The stability of capillary-gravity wave motion on horizontal free surface of viscous noncompressible fluid in the presence of magnetic surfactant in an external magnetic field was studied. It is shown that for normal as well as for tangential external magnetic field the horizontal free liquid surface is unstable for field strength exceeding some critical value that does not depend on the elastic constant of the surfactant film. However, for oblique external magnetic field the stability of the free surface depends not only on the field value but also on the surfactant elastic constant.

Mutual influence of wave motion and patterns of surfactant distribution

Patterns of wave propagation along the surface of a viscous liquid covered with an insoluble elastic surfactant film are studied analytically. The relationship between the damping decrement of capillary–gravitational waves and the distribution pattern of the surfactant concentration maxima relative to the crests of the waves is established as a function of the film’s elasticity.

Synergism of thiocyanate ions and microinterfacial surface as driving forces for heavy multi-metals extraction

A comprehensive study has been carried out to evaluate the extraction of heavy metals mixture (Co2+, Cr3+, Cu2+, Ni2+) from aqueous media by Winsor II non-ionic microemulsion, containing polyoxyethylene (4) lauryl ether as non-ionic surfactant and butyl acetate as organic phase. The extraction mechanism is based on the formation of thiocyanate complexes of metals and their transfer from aqueous to microemulsion phase, either towards the interfacial film of surfactant (Co2+) or into the core of micelles (Cr3+, Cu2+, Ni2+). The value of the distribution coefficient for Co2+ was higher than for the other studied metals and its extraction efficiency was not dependent on the working conditions, showing a maximum value (99.99%) in all cases. By using successive extractions, chromium, nickel and copper ions that remained in the aqueous phase after first extraction were transported into the microemulsion phase, leading to an increase in the extraction efficiency up to 99.99% for chromium and copper, and 85% for nickel. Based on pH influence, a selective extraction of Co2+ and Cr3+ can be achieved, since the cobalt ions were completely extracted into the microemulsion phase at pH = 1, and the chromium ions still remained in the aqueous phase.

Effect of Convection on Formation of Adsorbed Surfactant Film under Dynamic Change of Solution Surface Area

The dynamics of the formation of a surface phase in aqueous solutions of surfactants in a tray with the Langmuir barrier system during one compression–expansion cycle of the interface boundary is investigated both experimentally and theoretically. Organic salts of fatty acids such as potassium laurate, caprylate, and acetate, which are members of the same homologous series, were used as surfactants. It is experimentally determined that the dependence of the surface pressure increment measured under the maximum compression of the surface on the volume concentration has a maximum, the position of which is different for all the studied surfactant solutions. It is shown that the position of the maximum corresponds to the concentration value at which a saturated monolayer of surfactant molecules is formed at the interface boundary. A theoretical model that considers the effect of the forced convection arisen in the bulk of the solution upon changing the surface area is proposed for the interpretation of the experimental results. The model allows one to render the main kinetic characteristics of the adsorption/desorption processes involving the compounds under study. A good agreement between the theoretical and experimental results is observed, but there is a discrepancy between them when diffusion is considered to be the only way surfactant molecules are transferred into the bulk phase. Based on the data, a new method for determination of the Langmuir–Shishkovsky constant is proposed.

Ordering in Surfactant Foam Films Transferred onto Hydrophilic and Hydrophobic Substrates

Foam films have been formed by aqueous dodecyldimethylphosphine oxide (C12DMPO) and aqueous hexadecyltrimethylammonium bromide (C16TAB) solutions and drained. The surfactant films were transferred onto hydrophilic and hydrophobic substrates at five different drainage times. Angle-resolved X-ray photoelectron spectroscopy and metastable induced electron spectroscopy were used for investigation of the thickness and orientation of the surfactant molecules in the transferred foam film. Of the four combinations only the drained film formed by C16TAB transferred onto hydrophobic surfaces shows a strong degree of orientation of the surfactant molecules in the transferred film. The other three combinations do not show a preferred orientation of the surfactant molecules in the foam film. The phenomenon is discussed based on the interaction of the molecules within the films and the interaction of the formed films with the substrates.

Study of the influence of surfactants on the activity coefficients and mass transfer coefficients of methanol in aqueous mixtures by reversed-flow gas chromatography

This work focuses on the influences of surfactants on the activity coefficients, γ, of methanol in binary mixtures with water, as well as on the mass transfer coefficients, kc, for the evaporation of methanol, which is a ubiquitous component in the troposphere, from mixtures of methanol with water at various surfactant’s and methanol’s concentrations.The technique used is the Reversed-Flow Gas Chromatography (R.F.G.C.), a version of Inverse Gas Chromatography, which allows determining both parameters by performing only one experiment for the kc parameter and two experiments for the γ parameter. The kc and γ values decrease in the presence of the three surfactants used (CTAB, SDS, TRITON X-100) at all methanol’s and surfactant’s concentrations. The decrease in the methanol’s molar fraction, at constant number of surfactant films leads to a decrease in the kc and γ values, while the decrease in the surfactant’s concentration, at constant methanol’s molar fraction leads to an increase in both the kc and γ parameters.Mass transfer coefficients for the evaporation of methanol at the surfactant films, are also calculated which are approximately between 4 and 5 orders of magnitude larger than the corresponding mass transfer coefficients at the liquid films.Finally, thicknesses of the boundary layer of methanol in the mixtures of methanol with water were determined.The quantities found are compared with those given in the literature or calculated theoretically using various empirical equations. The precision of the R.F.G.C. method for measuring γ and kc parameters is approximately high (94.3–98.0%), showing that R.F.G.C. can be used with success not only for the thermodynamic study of solutions, but also for the interphase transport.

Characterization of Repulsive Forces and Surface Deformation in Thin Micellar Films via AFM.

Here we examine how the force on an atomic force microscope (AFM) tip varies as it approaches micellar surfactant films, and use this information to discern the film's surface structure and Young's modulus. Rows of wormlike hemimicelles were created at a graphite interface using 10 mM sodium dodecyl sulfate (SDS). We found that the repulsive force on a silicon nitride tip as it approached the surface was exponential, with a decay length of 2.0 ± 0.1 nm. The addition of Na2SO4 was found to cause a change in this behavior, with a clear split into two exponential regions at concentrations above 1 mM. We also observed that the range of these forces increased with added salt from ∼15 nm in pure SDS to ∼20 nm at a Na2SO4 concentration of 1.34 mM. These forces were inconsistent with electrostatic repulsion, and were determined to be steric in nature. We show that the behavior at higher salt concentrations is consistent with the theory of polyelectrolyte brushes in the osmotic regime. From this, we hypothesize the presence of micellar brushes at the surface that behave similarly to adsorbed polymer chains. In addition, the Young's modulus of the film was taken from data near the interface using Sneddon's model, and found to be 80 ± 40 MPa. Similar experiments were performed with 10 mM dodecylamine hydrochloride (DAH) solutions in the presence of added magnesium chloride. The decay length for the pure DAH solution was found to be 2.6 ± 0.3 nm, and the addition of 1.34 mM of MgCl2 caused this to increase to 3.7 ± 0.3 nm. No decay length splitting was observed for DAH. We conclude that the behavior at the surface resembles that of an uncharged polymer brush, as the ionic and surface charge densities are much lower for DAH than for SDS.

A simple technique for measuring the optical propagation losses in thin films

ABSTRACTA simple method for measuring the light propagation losses in thin films deposited on an transparent plane parallel substrate is described. It consists on measuring the scattered light intensity from a plane parallel waveguiding substrate on which the optical propagation loss measured thin film is deposited. The method is simple to set up and to operate. It allows to measure relatively large propagation losses. It is illustrated by measuring very large propagation losses in chromophore doped deoxyribonucleic – surfactant complex thin film deposited on a plane parallel glass plate. The method is particularly interesting for measuring large propagation losses.

Expression of surfactant protein B is dependent on cell density in H441 lung epithelial cells.

BackgroundExpression of surfactant protein (SP)-B, which assures the structural stability of the pulmonary surfactant film, is influenced by various stimuli, including glucocorticoids; however, the role that cell-cell contact plays in SP-B transcription remains unknown. The aim of the current study was to investigate the impact of cell-cell contact on SP-B mRNA and mature SP-B expression in the lung epithelial cell line H441.MethodsDifferent quantities of H441 cells per growth area were either left untreated or incubated with dexamethasone. The expression of SP-B, SP-B transcription factors, and tight junction proteins were determined by qPCR and immunoblotting. The influence of cell density on SP-B mRNA stability was investigated using the transcription inhibitor actinomycin D.ResultsSP-B mRNA and mature SP-B expression levels were significantly elevated in untreated and dexamethasone-treated H441 cells with increasing cell density. High cell density as a sole stimulus was found to barely have an impact on SP-B transcription factor and tight junction mRNA levels, while its stimulatory ability on SP-B mRNA expression could be mimicked using SP-B-negative cells. SP-B mRNA stability was significantly increased in high-density cells, but not by dexamethasone alone.ConclusionSP-B expression in H441 cells is dependent on cell-cell contact, which increases mRNA stability and thereby potentiates the glucocorticoid-mediated induction of transcription. Loss of cell integrity might contribute to reduced SP-B secretion in damaged lung cells via downregulation of SP-B transcription. Cell density-mediated effects should thus receive greater attention in future cell culture-based research.

Thickness-Dependent Order-to-Order Transitions of Bolaform-like Giant Surfactant in Thin Films

Controlling self-assembled nanostructures in thin films allows the bottom-up fabrication of ordered nanoscale patterns. Here we report the unique thickness-dependent phase behavior in thin films of a bolaform-like giant surfactant, which consists of butyl- and hydroxyl-functionalized polyhedral oligomeric silsesquioxane (BPOSS and DPOSS) cages telechelically located at the chain ends of a polystyrene (PS) chain with 28 repeating monomers on average. In the bulk, BPOSS-PS28-DPOSS forms a double gyroid (DG) phase. Both grazing incidence small-angle X-ray scattering and transmission electron microscopy techniques are combined to elucidate the thin film structures. Interestingly, films with thicknesses thinner than 200 nm exhibit an irreversible phase transition from hexagonal perforated layer (HPL) to compressed hexagonally packed cylinders (c-HEX) at 130 °C, while films with thickness larger than 200 nm show an irreversible transition from HPL to DG at 200 °C. The thickness-controlled transition pathway sug...

Design of pH-responsive “on-off” emulsions using CTAB/PPA emulsifiers by simulations and experiments

The pH-induced demulsification behaviors of “on-off” oil-in-water emulsions using cetyltrimethylammonium bromide (CTAB) and potassium phthalic acid (PPA) mixtures as emulsifiers were investigated by coarse-grained (CG) molecular dynamics (MD) simulations and experiments, aiming to design a new pH-responsive emulsion. On the one hand, we simulated the stability of emulsions of n-octane and aqueous CTAB/PPA solution, and phase diagrams of emulsion with different CTAB/PPA contents were observed at different pH. Furthermore, the demulsification processes from the low pH to high pH was investagated and clearly it began with film rupture and then accomplished with droplets fusion in few nanoseconds. Via analyzing the structure and molecular arrangment of the emulsion droplets, it was found that the reasons on pH-induced demulsification were weak hindrance effect of the surfactant film and electrostatic repulsion among emulsion droplets at high pH. On the other hand, through our experiments, the differences on stability of emulsions were verified and the reversible emulsification and demulsification processes by changing pH values were observed, which agreed well with our simulations. This work designed a new kind of pH-responsive emulsion using commercial surfactants CTAB/PPA by simulations and verified its pH-induced demulsification by experiments. It sets up a bridge between CG MD approach and experiment, which is expected to trigger further understanding and studies on stimuli responsive emulsion systems.

Pulmonary surfactant and bacterial lipopolysaccharide: the interaction and its functional consequences.

The respiratory system is constantly exposed to pathogens which enter the lungs by inhalation or via blood stream. Lipopolysaccharide (LPS), also named endotoxin, can reach the airspaces as the major component of the outer membrane of Gram-negative bacteria, and lead to local inflammation and systemic toxicity. LPS affects alveolar type II (ATII) cells and pulmonary surfactant and although surfactant molecule has the effective protective mechanisms, excessive amount of LPS interacts with surfactant film and leads to its inactivation. From immunological point of view, surfactant specific proteins (SPs) SP-A and SP-D are best characterized, however, there is increasing evidence on the involvement of SP-B and SP-C and certain phospholipids in immune reactions. In animal models, the instillation of LPS to the respiratory system induces acute lung injury (ALI). It is of clinical importance that endotoxin-induced lung injury can be favorably influenced by intratracheal instillation of exogenous surfactant. The beneficial effect of this treatment was confirmed for both natural porcine and synthetic surfactants. It is believed that the surfactant preparations have anti-inflammatory properties through regulating cytokine production by inflammatory cells. The mechanism by which LPS interferes with ATII cells and surfactant layer, and its consequences are discussed below.

The pH dependent interaction between nicotine and simulated pulmonary surfactant monolayers with associated molecular modelling

Pulmonary surfactant is an endogenous material that lines and stabilises the alveolar air–liquid interface. Respiratory mechanics can be compromised by exposure to environmental toxins such as cigarette smoke, which contains nicotine. This study aims to determine the influence of nicotine on the activity of simulated lung surfactant at pH 7 and pH 9. In all cases, the addition of nicotine to the test zone caused deviation in surfactant film performance. Importantly, the maximum surface pressure was reduced for each system. Computational modelling was applied to assess key interactions between each species, with the Gaussian 09 software platform used to calculate electrostatic potential surfaces. Modelling data confirmed either nicotine penetration into the two‐dimensional structure or interfacial/electrostatic interactions across the underside. The results obtained from this study suggest that nicotine can impair the ability of pulmonary surfactant to reduce the surface tension term, which can increase the work of breathing. When extrapolated to gross lung function, alveolar collapse and respiratory disease (e.g. chronic airway obstruction) may result. The delivery of nicotine to the (deep) lung can cause a deterioration in lung function and lead to reduced quality of life. Copyright © 2017 John Wiley & Sons, Ltd.

On the Morphology of the SDS Film on the Surface of Borosilicate Glass.

Surfactant films on solid surfaces have attracted much attention because of their scientific interest and applications, such as surface treatment agent, or for micro- or nano-scale templates for microfluidic devices. In this study, anionic surfactant sodium dodecyl sulfate (SDS) solutions with various charged inorganic salts was spread on a glass substrate and dried to form an SDS thin film. Atomic force microscopy (AFM) was employed to observe the micro-structure of the SDS thin film. The effects of inorganic salts on the morphology of the SDS film were observed and discussed. The results of experiments demonstrated that pure SDS film formed patterns of long, parallel, highly-ordered stripes. The existence of the inorganic salt disturbed the structure of the SDS film due to the interaction between the cationic ion and the anionic head groups of SDS. The divalent ion has greater electrostatic interaction with anionic head groups than that of the monovalent ion, and causes a gross change in the morphology of the SDS film. The height of the SDS bilayer measured was consistent with the theoretical value, and the addition of the large-sized monovalent ion would lead to lowering the height of the adsorbed structures.

The role of multilayers in preventing the premature buckling of the pulmonary surfactant

The pulmonary surfactant is a protein-lipid mixture that spreads into a film at the air-lung interface. The highly-compacted molecules of the film keep the interface from shrinking under the influence of otherwise high surface tension and thus prevent atelectasis. We have previously shown that for the film to withstand a high film pressure without collapsing it needs to assume a specific architecture of a molecular monolayer with islands of stacks of molecular multilayers scattered over the area. Surface activity was assessed in a captive bubble surfactometer (CBS) and the role of cholesterol and oxidation on surfactant function examined. The surfactant film was conceptualized as a plate under pressure. Finite element analysis was used to evaluate the role of the multilayer stacks in preventing buckling of the plate during compression. The model of film topography was constructed from atomic force microscope (AFM) scans of surfactant films and known physical properties of dipalmitoylphosphatidylcholine (DPPC), a major constituent of surfactant, using ANSYS structural-analysis software. We report that multilayer structures increase film stability. In simulation studies, the critical load required to induce surfactant film buckling increased about two-fold in the presence of multilayers. Our in vitro surfactant studies showed that surface topography varied between functional and dysfunctional films. However, the critical factor for film stability was the anchoring of the multilayers. Furthermore, the anchoring of multilayers and mechanical stability of the film was dependent on the presence of hydrophobic surfactant protein-C. The current study expands our understanding of the mechanism of surfactant inactivation in disease.

Investigation of the elastic and adhesion properties of adsorbed hydrophobically modified inulin films on latex particles using Atomic Force Microscopy (AFM)

Graft polymer surfactants provide very good colloidal stability because of strong steric repulsions between adsorbed surfactant films. The elastic and adhesion properties of adsorbed hydrophobically modified inulin polymer surfactant (INUTEC NRA) have been directly measured using Atomic Force Microscopy (AFM) measurements. For this purpose, poly(methyl methacrylate/butyl acrylate), P(MMA/BuA), latexes prepared in the presence of the hydrophobically modified inulin (INUTEC NRA) were used. These latexes (diameter 118nm and polydispersity index of 1.05) showed a very high colloidal stability in water and in the presence of electrolyte (up to 0.2moldm−3 KBr). The latexes were deposited on mica, which was silanated to enhance the adhesion of the latex particles to the surface. A silicon nitride tip with approximately 10nm diameter that also contained an adsorbed layer of surfactant was used in the AFM apparatus. The tip was allowed to approach, contact thereafter the particles with an applied force of 12.5nN, and finally detach from the film. Both elastic (Young’s) modulus of the film and adhesion force were studied. The results showed that the adsorbed surfactant films are highly elastic and their elastic modulus and adhesion force did not change significantly with the presence of Na2SO4 up to 0.05moldm−3. The high elastic contribution to the steric interaction ensures strong repulsion between the latex particles both in water and at high electrolyte concentrations. In addition, the lack of dependence of adhesion force on electrolyte concentration ensures uniform deposition of the latex particles on a flat substrate as for example in coating applications. These results show the advantages of using a graft polymer surfactant for enhancing the stability of particle suspensions, as illustrated in previous investigations.

Crystallisation of aspirin via simulated pulmonary surfactant monolayers and lung‐specific additives

Pain is a prevalent condition that can have a serious impact upon the socioeconomic function of a population. Numerous methods exist to administer analgesic medication (e.g. aspirin) to the body however inherent drawbacks limit patient acceptability. The inhaled route offers promise to facilitate the administration of medication to the body. Here, we consider the crystallisation behaviour of aspirin, our model therapeutic agent, when in contact with material of relevance to the lung. Thus, our approach aims to better understand the interaction between drug substances and the respiratory tract. Langmuir monolayers composed of a mixed surfactant system were supported on an aqueous subphase containing aspirin (7.5 mg/ml). The surfactant film was compressed to either 5mN/m (i.e. inhalation end point) or 50 mN/m (i.e. exhalation end point), whilst located within a humid environment for 16 h. Standard cooling crystallisation procedures were employed to produce control samples. Antisolvent crystallisation in the presence or absence of lung‐specific additives was conducted. All samples were analysed via scanning electron microscopy and X‐ray diffraction. Drug‐surfactant interactions were confirmed via condensed Langmuir isotherms. Scanning electron microscopy analysis revealed plate‐like morphology. The crystallisation route dictated both the crystal habit and particle size distribution. Dominant reflections were the (100) and (200) aspects. The main modes of interaction were hydrogen bonding, hydrophobic associations, and van der Waals forces. Here, we have demonstrated the potential of antisolvent crystallisation with lung‐specific additives to achieve control over drug crystal morphology. The approach taken can be applied in respirable formulation engineering. Copyright © 2017 John Wiley & Sons, Ltd.