The pH-Induced Specific Area Changes of Unsaturated Lipids Deposited onto a Bubble Interface.

In this work, we used an original experimental setup to examine the behavior of insoluble monolayers made with pH-sensitive lipids. Two kinds of unsaturated lipids were chosen: a cationic one (lipid 1) bearing an ammonium headgroup and an anionic one (lipid 2) terminated with an acidic phenol group. The lipids were deposited onto an air bubble interface maintained in an aqueous phase and, after stabilization, were subjected to a series of compressions performed at different pH values. These experiments disclosed a gradual increase in the specific area per molecule when lipids were neutralized. Imposing a pH variation at constant bubble volume also provided surface pressure profiles that confirmed this molecular behavior. As complementary characterization, dilatational rheology disclosed a phase transition from a purely elastic monophasic system to a viscoelastic two-phase system. We hypothesized that this unexpected increase in the specific area with lipid neutralization is related to the presence of unsaturations in each of the two branches of the hydrophobic tails that induce disorder, thereby increasing the molecular area at the interface. Application of the two-dimensional Volmer equation of state allowed the generation of quantitative values for the specific areas that showed variations with pH. It also allowed the determination of apparent pKa values, which are affected by both the electrostatic potential within the monolayer and the affinity of the lipid polar head for the aqueous phase.

Long-range hydrodynamic forces in liquid FM-AFM.

We study the effects of hydrodynamic forces in frequency-modulation AFM experiments (FM-AFM) in liquid. We first establish the theoretical equations needed to derive the interaction stiffness k int and the damping ß int due to the hydrodynamic forces from the frequency shift and the excitation amplitude. We develop specific FM-AFM experiments to measure the variation of k int and ß int over a large range of distance in water up to 200 µm. Comparison between theory and experiments point out that the evolution of k int at short and long distance arises from unsteady hydrodynamic forces on the cantilever. On the other hand, ß int is small at long distance and diverges at short probe-surface distance, as predicted by the classical Reynolds sphere model.

Pickering nano-emulsions stabilized by solid lipid nanoparticles as a temperature sensitive drug delivery system.

The development of biomaterials with low environmental impact has seen increased interest in recent years. In this field, lipid nanoparticles have found a privileged place in research and industry. The purpose of this study was to develop Pickering O/W nano-emulsions only stabilized by solid lipid nanoparticles (SLNs), as a new generation of safe, non-toxic, biocompatible, and temperature-sensitive lipid nano-carriers. The first part is dedicated to understanding the interfacial behavior of SLNs and their related stabilization mechanisms onto nano-emulsions formulated by ultrasonication. Investigations were focused on the surface coverage as a function of the SLN size and volume fraction of dispersed oil, in order to prove that the droplet stabilization is effectively performed by the nanoparticles, and to disclose the limitations of this formulation. Characterization is performed by dynamic light scattering and transmission electron microscopy. The second part of the study investigated SLN adsorption on a model oil/water interface (surface tension and rheology) through an axisymmetrical drop shape analysis (drop tensiometer), following the interfacial tension and the rheological behavior. The objective of this part is to characterize the phenomenon governing the droplet/interface interactions, and disclose the rheological behavior of the interfacial SLN monolayer. The effect of temperature was also investigated, proving a real destabilization of the nano-suspension when the sample is heated above a temperature threshold, impacting on the integrity of the SLNs, which partially melt, and strongly enhancing the release of a model drug (ketoprofen) encapsulated in the nano-emulsion oil core. To conclude, Pickering nano-emulsions only stabilized by SLNs appear to be a very efficient innovative drug nano-carrier, opening new doors as a potential temperature-sensitive drug delivery system.

Correction: Pickering nano-emulsions stabilized by solid lipid nanoparticles as a temperature sensitive drug delivery system.

Correction for 'Pickering nano-emulsions stabilized by solid lipid nanoparticles as a temperature sensitive drug delivery system' by Sidy Mouhamed Dieng et al., Soft Matter, 2019, DOI: 10.1039/c9sm01283d.

Pleomorphochaeta naphthae sp. nov., a new anaerobic fermentative bacterium isolated from an oil field.

A novel anaerobic fermentative bacterium, strain SEBR 4209T, was isolated from a water sample of a Congolese oil field. Strain SEBR 4209T is phylogenetically related to the genus Pleomorphochaeta, in the family Spirochaetaceae. Its closest relatives are Pleomorphochaeta caudata SEBR 4223T (94.5 % 16S rRNA gene sequence similarity) and Pleomorphochaeta multiformis MO-SPC2T (94.3 % similarity). Like the other members of this genus, cells have a pleomorphic morphology, in particular an annular shape and long stalks. Optimal growth was observed at 37 °C, at pH between 6.8 and 7.0, and with 40 g l-1 NaCl. This strain was only able to grow by fermentation of carbohydrates. The fermentation products from glucose utilization were acetate, ethanol, CO2 and H2. Predominant fatty acids were C14 : 0, C14 : 0 DMA, C16 : 0 and C16 : 1ω7c. The major polar lipids were phosphoglycolipids, phospholipids and glycolipids. The G+C content of the DNA was 29.6 mol%. Based on phenotypic characteristics and phylogenetic traits, strain SEBR 4209T is considered to represent a novel species of the genus Pleomorphochaeta, for which the name Pleomorphochaetanaphthae sp. nov. is proposed. The type strain is SEBR 4209T (=DSM 104684T=JCM 31871T).

Help from a Hindrance: Using Astigmatism in Round Capillaries To Study Contact Angles and Wetting Layers.

Round glass capillaries are a basic tool in soft-matter science, but often are shunned due to the astigmatism they introduce in micrographs. Here, we show how refraction in a capillary can be a help instead of a hindrance to obtain precise and sensitive information on two important interfacial properties: the contact angle of two immiscible fluids and the presence of thin films on the capillary wall. Understanding optical cusps due to refraction allows direct mesurement of the inner diameter of a capillary at the meniscus, which, with the height of the meniscus cap, determines the contact angle. The meniscus can thus be measured without intrusive additives to enhance visibility, such as dyes or calibrated particles, in uniform, curved, or even tapered capillaries or under demanding conditions not accessible by conventional methods, such as small volumes (µL), high temperatures, or high pressures. We further elicit the conditions for strong internal reflection on the inner capillary wall, involving the wall and fluid refractive indices and the wall thickness, and show how to choose the capillary section to detect thin (submicron) layers on the wall, by the contribution of total internal reflection to the cusps. As examples, we report the following: (i) CO2-water or -brine contact angles at glass interfaces, measured at temperatures and pressures up to 200 °C and 600 bar, revealing an effect apparently so far unreported-the decrease in the water-wet character of glass, due to dissolved salts in brine, is strongly reduced at high temperatures, where contact angles converge toward the values in pure water; (ii) A tenuous gas hydrate layer growing from the water-guest contact line on glass, invisible in transmission microscopy but prominent in the cusps due to total internal reflection.

Behavior of Marinobacter hydrocarbonoclasticus SP17 cells during initiation of biofilm formation at the alkane-water interface.

Hexadecane assimilation by Marinobacter hydrocarbonoclasticus SP17 occurs through the formation of a biofilm at the alkane-water interface. In this study we focused on the interactions of cells with the alkane-water interface occurring during initiation of biofilm development. The behavior of cells at the interface was apprehended by investigating alterations of the mechanical properties of the interface during cell adsorption, using dynamic drop tensiometry measurements. It was found that after having reached the hexadecane-water interface, by a purely thermal diffusion process, cells released surface-active compounds (SACs) resulting in the formation of an interfacial visco-elastic film. Release of SACs was an active process requiring protein synthesis. This initial interaction occurred on metabolizable as well as non-metabolizable alkanes, indicating that at this stage cells are not affected by the nature of the alkane forming the interface. In contrast, at a later stage, the nature of the interface turned out to exert control over the behavior of the cells. The availability of a metabolizable alkane at the interface influenced cell activity, as revealed by cell cluster formation and differences in the interfacial elasticity.

Cytoplasmic wax ester accumulation during biofilm-driven substrate assimilation at the alkane--water interface by Marinobacter hydrocarbonoclasticus SP17.

During growth on n-alkanes, the marine bacterium Marinobacter hydrocarbonoclasticus SP17 formed a biofilm at the alkane-water interface. We showed that hexadecane degradation was correlated with biofilm development and that alkane uptake is localized in the biofilm but not in the bulk medium. Biofilms were observed in cultures on metabolizable n-alkanes (C8-C28) and n-alcohols (C12 and C16), but were formed neither on non-metabolizable alkanes (pristane, heptamethylnonane and n-C32) nor on inert substrata (glass, polystyrene and Permanox). This substratum specificity indicates that biofilm formation is determined by the presence of an interface between an insoluble substrate and the aqueous phase. Simultaneously with biofilm growth, planktonic cells were released from the biofilm. Detached cells were in a non-growing state, implying that the growing population was exclusively located within the biofilm. Planktonic and sessile cells exhibited differences in their ultrastructure and lipid content. Biofilm cells contained a large amount of wax esters (0.47mg/mg protein) in rounded or irregularly shaped cytoplasmic inclusions, whereas detached cells displayed rod-shaped inclusions and contained 5 times fewer wax esters (0.10mg/mg protein) than their sessile counterparts. This study points out the inter-relationship between biofilm formation, insoluble substrate uptake and lipid storage.

Different surface corrugations occurring during drainage of axisymmetric thin liquid films.

This paper deals with the different surface corrugations observable during the thinning of axisymmetric thin and large aqueous films, stabilized by saponin. The films are observed using a thin film balance under a constant driving pressure. This device allows measurement of the thicknesses of the film surface shapes arising all along the drainage, as well as the following-up of their evolution before equilibrium is attained. Depending on the electrolyte (NaCl) concentration, three different sorts of corrugation were originally observed in such suspended thin liquid films. At the lowest NaCl concentrations, corresponding to repulsive potential between film walls, only the hydrodynamic corrugations deformed the film surfaces. Regarding the higher NaCl concentrations, when van der Waals forces become predominant, and following the thickness of the first-established thin film, the experiments disclose either that the thinner films are broken up by spinodal decomposition, or that the thicker ones are broken by nucleation and growth of black film. In addition, an original aspect of these works appears in the fact that these observations of the spontaneous decomposition of suspended thin films are relatively similar to those usually described for dewetting experiments on solid substrates, and are well fitted by the existing theoretical models.

Stability of water/crude oil emulsions based on interfacial dilatational rheology.

The dilatational viscoelasticity behaviors of water/oil interfaces formed with a crude oil and its distilled fractions diluted in cyclohexane were investigated by means of an oscillating drop tensiometer. The rheological study of the w/o interfaces at different frequencies has shown that the stable w/o emulsions systematically correspond to interfaces which present the rheological characteristics of a 2D gel near its gelation point. The stability of emulsions was found to increase with both the gel strength and the glass transition temperature of the gel. As expected, the indigenous natural surfactants responsible for the formation of the interfacial critical gel have been identified as the heaviest amphiphilic components present in the crude oil; i.e., asphaltenes and resins. Nevertheless, we have shown that such a gel can also form in the absence of asphaltene in the oil phase.

Properties of a two-dimensional asphaltene network at the water-cyclohexane interface deduced from dynamic tensiometry.

Static and dynamic tensiometries show that a newly prepared water/asphaltenated cyclohexane interface behaves as expected: the mean area occupied per asphaltene molecule is 2 nm2, and variations of interfacial tension and dilatational elastic modulus with time indicate that equilibrium is reached more slowly than that for usual surfactants. The use of the time/temperature superposition principle allows a detailed rheological study of a 2 day old interface of the same type which has reached equilibrium. It is found that the two-dimensional asphaltene network exhibits a glass transition zone, behaves as a gel near its gelation point, and is built by a universal process of aggregation.