Water-Repellent Galvanized Steel Surfaces Obtained by Sintering of Zinc Nanopowder.

Galvanized steel surfaces are widely used in industry as a solution to prevent corrosion of steel tools that operate in outdoor or corrosive and oxidative environments. These objects are coated with a zinc protective layer deposited by hot dip galvanization. Turning the surface of galvanized steel tools into superhydrophobic may lead to very useful functionalities, although it may be a difficult task, because the preservation of the thin zinc layer is a claim. We propose herein the use of a bottom-up approach based on sandblasting, followed by sintering of zinc nanoparticles on the galvanized steel substrate, which allowed us to produce a zinc-made hierarchical structure required for superhydrophobicity. These samples acquired a double-scale structure that led to superhydrophobicity when they were later hydrophobized with a thin fluoropolymer layer. We found that sandblasting might be useful but not mandatory, unlike the sintering process, which was essential to reach superhydrophobicity. We found that, under certain experimental conditions, the surfaces showed outstanding water-repellent properties. We observed that the sandblasting on galvanized steel caused more damage than the sintering process. Sintering of low-melting-point metal nanoparticles was revealed as a promising strategy to fabricate functional metallic surfaces.

In vitro Digestion of Emulsions in a Single Droplet via Multi Subphase Exchange of Simulated Gastrointestinal Fluids.

Emulsions are currently being used to encapsulate and deliver nutrients and drugs to tackle different gastrointestinal conditions such as obesity, nutrient fortification, food allergies, and digestive diseases. The ability of an emulsion to provide the desired functionality, namely, reaching a specific site within the gastrointestinal tract, inhibiting/retarding lipolysis, or facilitating digestibility, ultimately depends on its susceptibility to enzymatic degradation in the gastrointestinal tract. In oil-in-water emulsions, lipid droplets are surrounded by interfacial layers, where the emulsifiers stabilize the emulsion and protect the encapsulated compound. Achieving a tailored digestibility of emulsions depends on their initial composition but also requires monitoring the evolution of those interfacial layers as they are subjected to different phases of gastrointestinal digestion. A pendant drop surface film balance implemented with a multi-subphase exchange allows for simulating the in vitro digestion of emulsions in a single aqueous droplet immersed in oil by applying a customized static digestion model. The transit through the gastrointestinal tract is mimicked by the subphase exchange of the original droplet bulk solution with artificial media, mimicking the physiological conditions of each compartment/step of the gastrointestinal tract. The dynamic evolution of the interfacial tension is recorded in situ throughout the whole simulated gastrointestinal digestion. The mechanical properties of digested interfaces, such as interfacial dilatational elasticity and viscosity, are measured after each digestion phase (oral, gastric, small intestine). The composition of each digestive media can be tuned to account for the particularities of the digestive conditions, including gastrointestinal pathologies and infant digestive media. The specific interfacial mechanisms affecting proteolysis and lipolysis are identified, providing tools to modulate digestion by the interfacial engineering of emulsions. The obtained results can be manipulated for designing novel food matrices with tailored functionalities such as low allergenicity, controlled energy intake, and decreased digestibility.

Applications of serum albumins in delivery systems: Differences in interfacial behaviour and interacting abilities with polysaccharides.

One of the major applications of Serum Albumins is their use as delivery systems for lipophilic compounds in biomedicine. Their biomedical application is based on the similarity with Human Serum Albumin (HSA), as a fully biocompatible protein. In general, Bovine Serum Albumin (BSA) is treated as comparable to its human homologue and used as a model protein for fundamental studies since it is available in high amounts and well understood. This protein can act as a carrier for lipophilic compounds or as protective shell in an emulsion-based vehicle. Polysaccharides are generally included in these formulations in order to increase the stability and/or applicability of the carrier. In this review, the main biomedical applications of Albumins as drug delivery systems are first presented. Secondly, the differences between BSA and HSA are highlighted, exploring the similarities and differences between these proteins and their interaction with polysaccharides, both in solution and adsorbed at interfaces. Finally, the use of Albumins as emulsifiers for emulsion-based delivery systems, concretely as Liquid Lipid Nanocapsules (LLNs), is revised and discussed in terms of the differences encountered in the molecular structure and in the interfacial properties. The specific case of Hyaluronic Acid is considered as a promising additive with important applications in biomedicine. The literature works are thoroughly discussed highlighting similarities and differences between BSA and HSA and their interaction with polysaccharides encountered at different structural levels, hence providing routes to control the optimal design of delivery systems.

Effect of Hyaluronic Acid and Pluronic-F68 on the Surface Properties of Foam as a Delivery System for Polidocanol in Sclerotherapy.

The use of foams to deliver bioactive agents and drugs is increasing in pharmaceutics. One example is the use of foam as a delivery system for polidocanol (POL) in sclerotherapy, with the addition of bioactive compounds to improve the delivery system being a current subject of study. This work shows the influence of two bioactive additives on the structure and stability of POL foam: hyaluronic acid (HA) and Pluronic-F68 (F68). HA is a natural non-surface-active biopolymer present in the extracellular matrix while F68 is a surface-active poloxamer that is biocompatible with plasma-derived fluids. Both additives increase the bulk viscosity of the sample, improving foam stability. However, HA doubled and F68 quadruplicated the foam half lifetime of POL. HA reduced the size and polydispersity of the bubble size distribution and increased the surface elasticity with respect to POL. Both facts have a positive impact in terms of foam stability. F68 also altered bubble structure and increased surface elasticity, again contributing to the enhancement of foam stability. The surface characterization of these systems is important, as in foam sclerotherapy it is crucial to assure the presence of POL at the surface of the bubbles in order to deliver the sclerosant agent in the target vein.

Particles adsorbed at various non-aqueous liquid-liquid interfaces.

Particles adsorbed at liquid interfaces are commonly used to stabilise water-oil Pickering emulsions and water-air foams. The fundamental understanding of the physics of particles adsorbed at water-air and water-oil interfaces is improving significantly due to novel techniques that enable the measurement of the contact angle of individual particles at a given interface. The case of non-aqueous interfaces and emulsions is less studied in the literature. Non-aqueous liquid-liquid interfaces in which water is replaced by other polar solvents have properties similar to those of water-oil interfaces. Nanocomposites of non-aqueous immiscible polymer blends containing inorganic particles at the interface are of great interest industrially and consequently more work has been devoted to them. By contrast, the behaviour of particles adsorbed at oil-oil interfaces in which both oils are immiscible and of low dielectric constant (ε<3) is scarcely studied. Hydrophobic particles are required to stabilise these oil-oil emulsions due to their irreversible adsorption, high interfacial activity and elastic shell behaviour.

Topographic characterisation of dental implants for commercial use

BACKGROUND: To characterize the surface topography of several dental implants for commercial use. MATERIAL AND METHODS: Dental implants analyzed were Certain (Biomet 3i), Tissue Level (Straumann), Interna (BTI), MG-InHex (MozoGrau), SPI (Alphabio) and Hikelt (Bioner). Surface topography was ascertained using a confocal microscope with white light. Roughness parameters obtained were: Ra, Rq, Rv, Rp, Rt, Rsk and Rku. The results were analysed using single-factor ANOVA and Student-Neuman-Keuls (p< 0.05) tests. RESULTS: Certain and Hikelt obtained the highest Ra and Rq scores, followed by Tissue Level. Interna and SPI obtained lower scores, and MG-InHex obtained the lowest score. Rv scores followed the same trend. Certain obtained the highest Rp score, followed by SPI and Hikelt, then Interna and Tissue Level. MG-InHex obtained the lowest scores. Certain obtained the highest Rt score, followed by Interna and Hikelt, then SPI and Tissue Level. The lowest scores were for MG-InHex. Rsk was negative (punctured surface) in the MG-InHex, SPI and Tissue Level systems, and positive (pointed surface) in the other systems. Rku was higher than 3 (Leptokurtic) in Tissue Level, Interna, MG-InHex and SPI, and lower than 3 (Platykurtic) in Certain and Hikelt. CONCLUSIONS: The type of implant determines surface topography, and there are differences in the roughness parameters of the various makes of implants for clinical use

A simple strategy to improve the interfacial activity of true Janus gold nanoparticles: a shorter hydrophilic capping ligand.

Janus gold nanoparticles (JPs) of ∼4 nm-diameter half functionalized with 1-hexanethiol as a hydrophobic capping ligand exhibit significantly higher interfacial activity, reproducibility and rheological response when the other half is functionalized with 1,2-mercaptopropanediol (JPs-MPD) than with 2-(2-mercaptoethoxy)ethanol (JPs-MEE), both acting as hydrophilic capping ligands. The interfacial pressure measured by pendant drop tensiometry reaches 50 mN m(-1) and 35 mN m(-1) for the JPs-MPD at the water/air and water/decane interface, respectively. At the same area per particle, the JPs-MEE reveal significantly lower interfacial pressure: 15 mN m(-1) and 5 mN m(-1) at the water/air and water/decane interface, respectively. Interfacial dilatational rheology measurements also show an elastic shell behaviour at higher compression states for JPs-MPD while the JPs-MEE present near-zero elasticity. The enhanced interfacial activity of JPs-MPD is explained in terms of chemical and hydration differences between the MPD and MEE ligands, where MPD has a shorter hydrocarbon chain and twice as many hydroxyl terminal groups as MEE.

Surface activity of Janus particles adsorbed at fluid-fluid interfaces: Theoretical and experimental aspects.

Since de Gennes coined in 1992 the term Janus particle (JP), there has been a continued effort to develop this field. The purpose of this review is to present the most relevant theoretical and experimental results obtained so far on the surface activity of amphiphilic JPs at fluid interfaces. The surface activity of JPs at fluid-fluid interfaces can be experimentally determined using two different methods: the classical Langmuir balance or the pendant drop tensiometry. The second method requires much less amount of sample than the first one, but it has also some experimental limitations. In all cases collected here the JPs exhibited a higher surface or interfacial activity than the corresponding homogeneous particles. This reveals the significant advantage of JPs for the stabilization of emulsions and foams.

Natural Inhibitors of Lipase: Examining Lipolysis in a Single Droplet.

Inhibition of lipase activity is one of the approaches to reduced fat intake with nutritional prevention promoting healthier diet. The food industry is very interested in the use of natural extracts, hence reducing the side effects of commercial drugs inhibiting lipolysis. In this work we propose a novel methodology to rapidly assess lipolysis/inhibition in a single droplet by interfacial tension and dilatational elasticity. The evolution of the interfacial tension of lipase in simplified duodenal fluid in the absence and that in the presence of the pharmaceutical drug Xenical are the negative (5 ± 1 mN/m) and positive (9 ± 1 mN/m) controls of the inhibition of lipolysis, respectively. Then, we correlate the inhibition with the reduction of the interfacial activity of lipase and further identify the mode of action of the inhibition based on dilatational response (conformational changes induced in the molecule/blocking of adsorption sites). This work provides new insight into the lipase inhibition mechanism and a rapid methodology to identify the potential of new natural inhibitors.

Interfacial Activity and Contact Angle of Homogeneous, Functionalized, and Janus Nanoparticles at the Water/Decane Interface.

Surface heterogeneity affects the behavior of nanoparticles at liquid interfaces. To gain a deeper understanding on the details of these phenomena, we have measured the interfacial activity and contact angle at water/decane interfaces for three different types of nanoparticles: homogeneous poly(methyl methacrylate) (PMMA), silica functionalized with a capping ligand containing a methacrylate terminal group, and Ag-based Janus colloids with two capping ligands of different hydrophobicity. The interfacial activity was analyzed by pendant drop tensiometry, and the contact angle was measured directly by freeze-fracture shadow-casting cryo-scanning electron microscopy. The silver Janus nanoparticles presented the highest interfacial activity, compared to the silica nanoparticles and the homogeneous PMMA nanoparticles. Additionally, increasing the bulk concentration of the PMMA and silica nanoparticles up to 100-fold compared to the Janus nanoparticles led to silica particles forming fractal-like structures at the interface, contrary to the PMMA particles that did not show any spontaneous adsorption.

Improved digestibility of ß-lactoglobulin by pulsed light processing: a dilatational and shear study.

Modifying the protein conformation appears to improve the digestibility of proteins in the battle against allergies. However, it is important not to lose the protein functionality in the process. Light pulse technology has been recently tested as an efficient non-thermal process which alters the conformation of proteins while improving their functionality as stabilizers. Also, in order to rationally design emulsion based food products with specific digestion profiles, we need to understand how interfacial composition influences the digestion of coated interfaces. This study has been designed to investigate the effects of pulsed light (PL) treatment on the gastrointestinal digestion of protein covered interfaces. We have used a combination of dilatational and shear rheology which highlights inter and intra-molecular interactions providing new molecular details on protein digestibility. The in vitro digestion model analyses sequentially pepsinolysis, trypsinolysis and lipolysis of ß-lactoglobulin (BLG) and pulsed light treated ß-lactoglobulin (PL-BLG). The results show that the PL-treatment seems to facilitate digestibility of the protein network, especially regarding trypsinolysis. Firstly, PL treatment just barely enhances the enzymatic degradation of BLG by pepsin, which dilutes and weakens the interfacial layer, due to increased hydrophobicity of the protein owing to PL-treatment. Secondly, PL treatment importantly modifies the susceptibility of BLG to trypsin hydrolysis. While it dilutes the interfacial layer in all cases, it strengthens the BLG and weakens the PL-BLG interfacial layer. Finally, this weakening appears to slightly facilitate lipolysis as evidenced by the results obtained upon addition of lipase and bile salts (BS). This research allows identification of the interfacial mechanisms affecting enzymatic hydrolysis of proteins and lipolysis, which demonstrates an improved digestibility of PL-BLG. The fact that PL treatment did not affect the functionality of the protein makes it a valuable alternative for tailoring novel food matrices with improved functional properties such as decreased digestibility, controlled energy intake and low allergenicity.

Comparison of the interfacial activity between homogeneous and Janus gold nanoparticles by pendant drop tensiometry.

The interfacial activity of 3.5 nm homogeneous (HPs) and amphiphilic Janus gold nanoparticles (JPs) was characterized by pendant drop tensiometry for water/air and water/decane interfaces. This technique requires a smaller quantity of nanoparticles than the traditional Langmuir balance technique. The direct deposition at the interface of the nanoparticles dispersed in a spreading solvent also requires smaller quantities of sample than does adsorption from the bulk. From the growing and shrinking of the pendant drops, the interfacial activity of the nanoparticles can be evaluated and compared within a wide range of area per particle. In this work, the JPs exhibited a higher interfacial activity than did the HPs in all cases. A hard disk model fits the piecewise compression isotherm of the HPs, yet this model underestimates the interactions between the JPs adsorbed at the interface.

Dynamic contact angle and spreading rate measurements for the characterization of the effect of dentin surface treatments.

A new methodology capable of providing reliable and reproducible contact angle (theta) data has been employed to study the effect of clinical treatments grinding, acid etching, and deproteinization on medial dentin tissue. It is based on the application of the ADSA-CD algorithm to the determination of low-rate dynamic contact angles, obtained from slowly growing drops, and on contact angle measurement, as well as spreading behavior analysis, during the relaxation of the system (water on treated dentin) after initial drop growth. The theta data obtained were substantially more reproducible than those obtained with classical methods. A net effect of the treatment on theta was found, increasing dentin wettability: theta (polished) >theta (etched) >theta (deproteinized). The spreading rates correlate with the angles and are adequate for the dentin surface characterization. ANOVA and SNK tests show that for advancing contact angles the means corresponding to all treatments are significantly different. In the relaxing phase, mean angle and spreading rates on polished dentin differ significantly from those on etched and deproteinized dentin, but the latter do not differ significantly from each other.

Electrokinetic parameters of colloidal model systems: analysis and comparison between dilute and concentrated dispersions.

In the last decades, the interest of many scientists has been focused on the atypical electrokinetic behavior of charged colloidal systems since several studies have shown, in most cases; it is not so ideal as expected. Particularly, two interesting phenomena have not been clearly explained yet. First, the zeta potential magnitude does not decrease monotonically with increasing ionic strength, as expected according to the Gouy-Chapmann model predicts. Second, the zeta potential obtained from different techniques shows discrepancies. More specifically, the zeta potential obtained from streaming potential is lower (in absolute value) than that measured through electrophoretic mobility. However, a recent work has pointed out that these discrepancies seem to disappear if certain conditions (related with the surface charge density) are satisfied. This work also revealed that unexpected results are found when the electric conductivity was used. Spherical polystyrene particles of appropriate particle size and charge density are employed as polymeric colloidal model in the present work. Common and adequate models are used to make clear and easy our theoretical analysis and its interpretation. To test the surface conductance and ionic mobility effects at the solid-liquid interface, both water medium and alcohol-water mixtures are used.