Simple Method for Rheological Determination of Surfactant Layer Thickness, Adsorbed on Soft Rubber Particles.

Natural rubber latex is a colloidal suspension of particles, which is very important for many industrial applications. These latex particles are not only polydispersed but also very soft and deformable, which makes the prediction of rheological properties much difficult. Herein, the rheology of natural rubber latex has been studied at high particle concentrations, analyzing the effects of surfactant addition on colloidal stability. A hydrophobically modified inulin surfactant (INUTEC NRA) was selected for this study since previous works had shown that this inulin surfactant imparts good colloidal stability to polystyrene latex particles. The most important objective was studying the influence of the surfactant on the particle adsorbed layer and determining the thickness of the adsorbed surfactant layer. The results showed that the relative viscosity increased as a function of latex volume fraction, and this increase became extremely sharp as the volume fraction approached the maximum packing volume fraction, as expected. This variation in viscosity with the volume fraction has a complex behavior, which could not be analyzed using conventional models based on hard rigid spheres, such as Krieger-Dougherty (K-D) or Maron-Pierce (M-P). Herein, we describe a simple semiempirical method to determine the surfactant adsorbed layer thickness, based on the linear dependence of intrinsic viscosity with 1/(ϕmax - ϕ)2, where ϕ is the volume fraction of rubber particles and ϕmax is the maximum volume fraction at which viscosity tends to infinity. The difference in the maximum packing fraction, with and without the surfactant, allows the calculation of the adsorbed layer thickness, δ ≈ 2.8 nm, which is a good estimate for the thickness of surfactant molecules adsorbed on latex particles. This surfactant thickness has been confirmed by direct measurements using dynamic light scattering (DLS), which gave a value of 3.1 nm. Viscoelastic oscillatory measurements have also been performed, showing that natural rubber particle suspensions are predominantly elastic above ϕ = 0.63 latex volume fractions. The elastic modulus has been analyzed as a function of surfactant concentration, confirming that the stability of latex particles is mainly controlled by the surfactant concentration.

Gelatin/Maltodextrin Water-in-Water (W/W) Emulsions for the Preparation of Cross-Linked Enzyme-Loaded Microgels.

Cross-linked gelatin microgels were formed in gelatin-in-maltodextrin water-in-water (W/W) emulsions and evaluated as carriers of the enzyme ß-galactosidase (ß-Gal). The phase behavior of aqueous gelatin/maltodextrin mixtures was studied in detail, focusing on the multiphase region of the phase diagram that is constituted by three equilibrium phases: two immiscible aqueous phases plus one solid phase. The solid phase was analyzed by Raman spectroscopy, and water-in-water emulsions were formed within the multiphase region. Gelation of the dispersed gelatin droplets was induced by cooling and cross-linking with genipin, which is a natural cross-linking reagent of low toxicity, leading to the formation of gelatin microgel particles. These microgels were studied as delivery vehicles for the enzyme lactase, used as a model active component. Various incorporation methods of the enzyme were tested, to achieve highest encapsulation yield and activity recovery. Microgel particles, loaded with the enzyme, can be freeze-dried, and the enzyme remained active after a complete cycle of freeze-drying and rehydration. The stability of the enzyme at 37 °C under gastric and neutral pH conditions was tested and led to the conclusion that the cross-linked microgels could be suitable for use in food-industry, where ß-Gal carriers are of interest for hydrolyzing lactose in milk products.

Antagonistic effects between magnetite nanoparticles and a hydrophobic surfactant in highly concentrated Pickering emulsions.

Herein we present a systematic study of the antagonistic interaction between magnetite nanoparticles (Fe3O4) and nonionic hydrophobic surfactant in Pickering highly concentrated emulsions. Interfacial tension measurements, phase behavior, and emulsion stability studies, combined with electron microscopy observations in polymerized systems and magnetometry, are used to support the discussion. First, stable W/O highly concentrated emulsions were obtained using partially hydrophobized magnetite nanoparticles. These emulsions experienced phase separation when surfactant is added at concentrations as low as 0.05 wt %. Such phase separation arises from the preferential affinity of the surfactant for the nanoparticle surfaces, which remarkably enhances their hydrophobicity, leading to a gradual desorption of nanoparticles from the interface. W/O emulsions were obtained at higher surfactant concentrations, but in this case, these emulsions were mainly stabilized by surfactant molecules. Therefore, stable emulsions could be prepared in two separate ranges of surfactant concentrations. After polymerization, low-density macroporous polymers were obtained, and the adsorption and aggregation of nanoparticles was analyzed by transmission electron microscopy. The progressive displacement of the nanoparticles was revealed: from the oil-water interface, in which aggregated nanoparticles were adsorbed, forming dense layers, to the continuous phase of the emulsions, where small nanoparticle aggregates were randomly dispersed. Interestingly, the results also show that the blocking temperature of the iron oxide superparamagnetic nanoparticles embedded in the macroporous polymers could be modulated by appropriate control of the concentrations of both surfactant and nanoparticles.

Facile synthesis of meso/macroporous dual materials with ordered mesopores using highly concentrated emulsions based on a cubic liquid crystal.

A new simple one-step method has been developed to obtain SiO(2) monolithic materials with a bimodal meso- and macroporous pore-size distribution. Sol-gel reactions were carried out in the continuous phase of highly concentrated emulsions with a cubic liquid crystal in this external phase, using a polyoxyethylene alkyl ether surfactant and containing a novel glycol-modified silane, tetra(2-hydroxyethyl) orthosilicate (abbreviated as THEOS). The hydrolysis and condensation reactions of this precursor have been carried out in basic pH, between pH 8.8 and 11.4. Interestingly, the ethylene glycol released during condensation reactions does not affect significantly the structure of the cubic liquid crystalline phase, which was stable during the sol-gel reactions. As a result, the cubic phase based emulsions could template the formation of meso/macroporous dual materials, which possess interconnected polydisperse macropores, between 1 and 5 µm, and cubic-ordered mesopores, with a narrow pore size distribution around 4 nm. Monoliths with a specific surface area higher than 550 m(2) g(-1) and bulk density of 0.16 g cm(-3) have been obtained.

Conductive microemulsions for template CoNi electrodeposition.

Microemulsions have been revealed as feasible templates to grow magnetic nanostructures using an electrodeposition method. Reducing agents are not required and the applied potential has been used as driving force of the nanostructure growth. A systematic study of conductive microemulsion systems to allow the CoNi electrodeposition process has been performed. Different surfactants and organic components have been tested to form microemulsions with a CoNi electrolytic bath as an aqueous component in order to define the microemulsions showing enough conductivity to perform an electrodeposition process from the aqueous component. By using microemulsions of the aqueous electrolyte solution-Triton X-100-diisopropyl adipate system, CoNi electrodeposition has been achieved, the structure of the deposits being dependent on the composition and structure of the microemulsion, which can act as a soft-template to obtain different discontinuous deposits. The magnetic properties of the CoNi deposits vary with their structure.

EHO-85, Novel Amorphous Antioxidant Hydrogel, Containing Olea europaea Leaf Extract-Rheological Properties, and Superiority over a Standard Hydrogel in Accelerating Early Wound Healing: A Randomized Controlled Trial.

Many advanced wound healing dressings exist, but there is little high-quality evidence to support them. To determine the performance of a novel amorphous hydrogel (EHO-85) in relation to its application, we compared its rheological properties with those of other standard hydrogels (SH), and we assessed the induction of acceleration of the early stages of wound healing as a secondary objective of a prospective, multicenter, randomized, observer-blinded, controlled trial. The patients were recruited if they had pressure, venous, or diabetic foot ulcers and were treated with EHO-85 (n = 103) or VariHesive® (SH) (n = 92), and their response was assessed by intention-to-treat as wound area reduction (WAR (%)) and healing rate (HR mm2/day) in the second and fourth weeks of treatment. Results: EHO-85 had the highest shear thinning and G'/G″ ratio, the lowest viscous modulus, G″, and relatively low cohesive energy; EHO-85 had a significantly superior effect over SH in WAR and HR, accelerating wound healing in the second and fourth weeks of application (p: 0.002). This superiority is likely based on its optimal moisturizing capacity and excellent pH-lowering and antioxidant properties. In addition, the distinct shear thinning of EHO-85 facilitates spreading by gentle hand pressure, making it easier to apply to wounds. These rheological properties contribute to its improved performance.

Preparation of mesoporous/macroporous materials in highly concentrated emulsions based on cubic phases by a single-step method.

A novel and simple single-step method for the preparation of meso/macroporous silica materials is described, which consists in templating in highly concentrated emulsions with a cubic liquid crystal in the continuous phase. Tetraethyl orthosilicate (TEOS) was solubilized in the aqueous continuous phase of highly concentrated emulsions stabilized by C(12)(EO)(8) and a PEO-PPO-PEO block copolymer nonionic surfactant, with a cubic liquid crystalline phase of the Fd3m type. The resulting silica materials were characterized by small-angle X-ray scattering, nitrogen sorption and transmission electron microscopy. The results showed that a dual pore size distribution was obtained, consisting of mesopores in the nanometer range and macropores between 1 and 5 µm. These dual meso/macroporous silicas with bimodal pore size distribution can possess specific surface areas higher than 400 m(2)/g.

Physicochemical characterization of natural-like branched-chain glycosides toward formation of hexosomes and vesicles.

Synthetic branched-chain glycolipids have become of great interest in biomimicking research, since they provide a suitable alternative for natural glycolipids, which are difficult to extract from natural resources. Therefore, branched-chain glycolipids obtained by direct syntheses are of utmost interest. In this work, two new branched-chain glycolipids are presented, namely, 2-hexyldecyl ß(α)-D-glucoside (2-HDG) and 2-hexyldecyl ß(α)-D-maltoside (2-HDM) based on glucose and maltose, respectively. The self-assembly properties of these glycolipids have been studied, observing the phase behavior under thermotropic and lyotropic conditions. Due to their amphiphilic characteristics, 2-HDG and 2-HDM possess rich phase behavior in dry form and in aqueous dispersions. In the thermotropic study, 2-HDG formed a columnar hexagonal liquid crystalline phase, whereas in a binary aqueous system, 2-HDG formed an inverted hexagonal liquid crystalline phase in equilibrium with excess aqueous solution. Furthermore, aqueous dispersions of the hexagonal liquid crystal could be obtained, dispersions known as hexosomes. On the other hand, 2-HDM formed a lamellar liquid crystalline phase (smectic A) in thermotropic conditions, whereas multilamellar vesicles have been observed in equilibrium with aqueous media. Surprisingly, 2-HDM mixed with sodium dodecyl sulfate or aerosol OT induced the formation of more stable unilamellar vesicles. Thus, the branched-chain glycolipids 2-HDG and 2-HDM not only provided alternative nonionic surfactants with rich phase behavior and versatile nanostructures, but also could be used as new drug carrier systems in the future.

Oil-in-alcohol highly concentrated emulsions as templates for the preparation of macroporous materials.

New oil-in-alcohol highly concentrated emulsions were formulated and were used as a templates to obtain macroporous poly(furfuryl alcohol) monoliths by a one-step method. The oil-in-alcohol highly concentrated emulsions were prepared by stepwise addition of the oil phase to the surfactant-alcohol solution and were characterized by optical microscopy and by laser diffraction. The typical structure of highly concentrated emulsions, with close-packed polyhedral droplets, has been observed. Poly(furfuryl alcohol) monoliths were obtained by polymerizing in the external phase of these emulsions. These materials are mainly macroporous and retain the size distribution and morphology from the highly concentrated emulsions. The internal structure of the monoliths was observed by scanning electron microscopy. The images showed an interconnected network with pore size similar to the droplet size of the highly concentrated emulsions used as templates.

Drug delivery properties of macroporous polystyrene solid foams.

PURPOSE: Polymeric porous foams have been evaluated as possible new pharmaceutical dosage forms. METHODS: These materials were obtained by polymerization in the continuous phase of highly concentrated emulsions prepared by the phase inversion temperature method. Their porosity, specific surface and surface topography were characterized, and the incorporation and release of active principles was studied using ketoprofen as model lipophilic molecule. RESULTS: Solid foams with very high pore volume, mainly inside macropores, were obtained by this method. The pore morphology of the materials was characterized, and very rough topography was observed, which contributed to their nearly superhydrophobic properties. These solid foams could be used as delivery systems for active principles with pharmaceutical interest, and in the present work ketoprofen was used as a model lipophilic molecule. CONCLUSIONS: Drug incorporation and release was studied from solid foam disks, using different concentrations of the loading solutions, achieving a delayed release with short lag-time.

Macroporous polymers obtained in highly concentrated emulsions stabilized solely with magnetic nanoparticles.

Magnetic macroporous polymers have been successfully prepared using Pickering high internal phase ratio emulsions (HIPEs) as templates. To stabilize the HIPEs, two types of oleic acid-modified iron oxide nanoparticles (NPs) were used as emulsifiers. The results revealed that partially hydrophobic NPs could stabilize W/O HIPEs with an internal phase above 90%. Depending upon the oleic acid content, the nanoparticles showed either an arrangement at the oil-water interface or a partial dispersion into the oil phase. Such different abilities to migrate to the interface had significant effects on the maximum internal phase fraction achievable and the droplet size distribution of the emulsions. Highly macroporous composite polymers were obtained by polymerization in the external phase of these emulsions. The density, porosity, pore morphology and magnetic properties were characterized as a function of the oleic acid content, concentration of NPs, and internal phase volume of the initial HIPEs. SEM imaging indicated that a close-cell structure was obtained. Furthermore, the composite materials showed superparamagnetic behavior and a relatively high magnetic moment.

All-Aqueous Liquid Crystal Nanocellulose Emulsions with Permeable Interfacial Assembly.

We report on the formation of water-in-water liquid crystal emulsions with permeable colloidal assemblies. Rodlike cellulose nanocrystals (CNC) spontaneously self-assemble into a helical arrangement with the coexistence of nonionic, hydrophilic polyethylene glycol (PEG) and dextran, whereas the two polymer solutions are thermodynamically incompatible. Stable water-in-water emulsions are easily prepared by mixing the respective CNC/polymer solutions, showing micrometric CNC/PEG dispersed droplets and a continuous CNC/dextran phase. With time, the resulting emulsion demixes into an upper, droplet-lean isotropic phase and a bottom, droplet-rich cholesteric phase. Owing to the osmotic pressure gradient between PEG and dextran phases, target transfer of cellulose nanoparticles occurs across the water/water interface to reassemble into a liquid crystal-in-liquid crystal emulsion with global cholesteric organization. The observed structural, optical, and temporal evolution confirm that the colloidal particles in the two immiscible phases experience short-range interactions and form long-range assemblies across the interface.

Short and ultrashort antimicrobial peptides anchored onto soft commercial contact lenses inhibit bacterial adhesion.

Commercial soft contact lenses were chemically modified to incorporate antibacterial properties. Contact lenses and especially soft contact lenses present a risk of eye microbial infection that eventually may lead to vision loss. This is a significant health issue given the large population of contact lenses wearers worldwide. In order to introduce bactericidal activity in hydrogel contact lenses, one short and one ultrashort antimicrobial peptides, LKKLLKLLKKLLKL (LK) and IRIRIRIR (IR), were selected. These peptides were anchored on the surface of contact lenses using a linker (1,4-butanediol diglycidyl ether) under mild conditions (room temperature, pH = 7.4). Physical and chemical properties of peptide-functionalized contact lenses were investigated through several analytical techniques including wettability, Raman confocal microscopy, fluorescence studies, refractometry and spectrophotometry. These studies demonstrated that contact lens modification occurred at the nanolevel (ng/lens). Bacterial cultures showed that peptide-functionalized contact lenses can drastically reduce bacterial adhesion and viability when exposed to Pseudomonas aeruginosa and Staphylococcus aureus. These systems offer the potential to minimise corneal bacterial infection and represent a suitable platform for future ophthalmic devices.

Formulating stable hexosome dispersions with a technical grade diglycerol-based surfactant.

We report on the phase behavior of a technical grade and commercially available diglycerol monoisostearate, C41V, and its use for the preparation of nanostructured liquid crystal dispersions (hexosomes). C41V in water forms a reverse hexagonal liquid crystal at room temperature and in a wide range of concentrations (0.5-95 wt%); this hexagonal liquid crystal is stable up to 70 °C. A simple and effective method has been developed to disperse hexosomes with an encapsulated active molecule (Ketoprofen) that consists of (1) producing a nano-emulsion stabilized by an amphiphilic block copolymer (Pluronic F127) and containing ethyl acetate and C41V by using ultrasounds and (2) evaporating the solvent to produce hexosomes. The size of the hexosomes and ultrasound dispersion time is markedly reduced by using ethyl acetate as an auxiliary solvent with an optimal initial ratio of C41V:ethyl acetate of 50:50. Dynamic light scattering shows that the size of the hexosomes decreases as the concentration of stabilizer F127 or encapsulated Ketoprofen is increased. The lattice parameter in the hexagonal structure is calculated from small angle scattering data to be ca. 5.3  nm and is only slightly dependent on the amount of F127 and/or encapsulated Ketoprofen. Cryo electron microscopy reveals that the samples contain hexosomes and these coexist with spherical, likely F127 micelles. Lastly, hexosomes show a pH responsive release of Ketoprofen which could be useful for target delivery in the gastrointestinal tract.

Viscoelastic properties of polystyrene and poly(methyl methacrylate) dispersions sterically stabilized by hydrophobically modified inulin (polyfructose) polymeric surfactant.

Recently, steric repulsive forces induced by a new graft copolymer surfactant, which is based in inulin (polyfructose), have been described. Previous investigations by atomic force microscopy between solid surfaces covered with adsorbed surfactant indicated strong repulsive forces even at high electrolyte concentration, due to the steric repulsion produced by the surfactant hydration. In the present paper, the colloidal stabilization provided by this surfactant is studied by rheology. The measurements were carried out on sterically stabilized polystyrene (PS) and poly(methyl methacrylate) (PMMA) containing adsorbed surfactant (INUTEC SP1). Steady-state shear stress as a function of shear rate curves was established at various latex volume fractions. The viscosity volume fraction curves were compared with those calculated using the Doughtry-Krieger equation for hard sphere dispersions. From the experimental eta r-phi curves the effective volume fraction of the latex dispersions could be calculated and this was used to determine the adsorbed layer thickness Delta. The value obtained was 9.6 nm, which is in good agreement with that obtained using atomic force microscopy (AFM). Viscoelastic measurements of the various latex dispersions were carried out as a function of applied stress (to obtain the linear viscoelastic region) and frequency. The results showed a change from predominantly viscous to predominantly elastic response at a critical volume fraction (phi c). The effective critical volume fraction, phi eff, was calculated using the adsorbed layer thickness (Delta) obtained from steady-state measurements. For PS latex dispersions phi eff was found to be equal to 0.24 whereas for PMMA phi eff=0.12. These results indicated a much softer interaction between the latex dispersions containing hydrated polyfructose loops and tails when compared with latices containing poly(ethylene oxide) (PEO) layers. The difference could be attributed to the stronger hydration of the polyfructose loops and tails when compared with PEO. This clearly shows the much stronger steric interaction between particles stabilized using hydrophobically modified inulin.

Interaction forces between particles stabilized by a hydrophobically modified inulin surfactant.

The adsorption isotherm of a hydrophobically modified inulin (INUTEC SP1) on polystyrene (PS) and poly(methyl methacrylate) (PMMA) particles was determined. The results show a high affinity isotherm for both particles as expected for a polymeric surfactant adsorption. The interactions forces between two layers of the hydrophobically modified inulin surfactant adsorbed onto a glass sphere and plate was determined using a modified atomic force microscope (AFM) apparatus. In the absence of any polymer, the interaction was attractive although the energy of interaction was lower than predicted by the van der Waals forces. The results between two layers of the adsorbed polymer confirms the adsorption isotherms results and provides an explanation to the high stability of the particles covered by INUTEC SP1 at high electrolyte concentration. Stability of dispersions against strong flocculation could be attributed to the conformation of the polymeric surfactant at the solid/liquid interface (multipoint attachment with several loops) which remains efficient at Na(2)SO(4) concentration reaching 1.5 mol dm(-3). The thickness of the adsorbed polymer layer in water determined both by AFM and rheology measurements, was found to be about 9 nm.

Phase behavior and preparation of mesoporous silica in aqueous mixtures of fluorinated surfactant and hydrophobic fluorinated polymer.

The phase behavior and formation of self-assemblies in the ternary water/fluorinated surfactant (C(8)F(17)EO(10))/hydrophobic fluorinated polymer (C(3)F(6)O)(n)COOH system and the application of those assemblies in the preparation of mesostructured silica have been investigated by means of phase study, small angle X-ray scattering, and rheology. Hexagonal (H(1)), bicontinuous cubic (V(1)) with Ia3d symmetry, and polymer rich lamellar (L(alpha)(')) are observed in the ternary diagram. C(8)F(17)EO(10) molecules are dissolved in polymer rich aggregates, whereas (C(3)F(6)O)(n)COOH molecules are practically insoluble in the surfactant lamellar phase due to packing restrictions. Hence, two types of lamellar phases exist: one with surfactant rich (L(alpha)) and the other with polymer rich (L(alpha)(')) in the water/C(8)F(17)EO(10)/(C(3)F(6)O)(n)COOH system. As suggested by rheological measurements, worm-like micelles are present in C(8)F(17)EO(10) aqueous solutions but a rod-sphere transition takes place by solubilization of (C(3)F(6)O)(n)COOH. C(8)F(17)EO(10) acts as a structure directing agent for the preparation of hexagonal mesoporous silica by the precipitation method. The addition of (C(3)F(6)O)(n)COOH induces the formation of larger but disordered pores.

The influence of surfactant mixing ratio on nano-emulsion formation by the pit method.

The formation of O/W nano-emulsions by the PIT emulsification method in water/mixed nonionic surfactant/oil systems has been studied. The hydrophilic-lipophilic properties of the surfactant were varied by mixing polyoxyethylene 4-lauryl ether (C12E4) and polyoxyethylene 6-lauryl ether (C12E6). Emulsification was performed in samples with constant oil concentration (20 wt%) by fast cooling from the corresponding HLB temperature to 25 degrees C. Nano-emulsions with droplet radius 60-70 nm and 25-30 nm were obtained at total surfactant concentrations of 4 and 8 wt%, respectively. Moreover, droplet size remained practically unchanged, independent of the surfactant mixing ratio, X(C12E6). At 4 wt% surfactant concentration, the polydispersity and instability of nano-emulsions increased with the increase in X(C12E6). However, at 8 wt% surfactant concentration, nano-emulsions with low polydispersity and high stability were obtained in a wide range of surfactant mixing ratios. Phase behavior studies showed that at 4 wt% surfactant concentration, three-liquid phases (W+D+O) coexist at the starting emulsification temperature. Furthermore, the excess oil phase with respect to the microemulsion D-phase increases with the increase in X(C12E6), which could explain the increase in instability. At 8 wt% surfactant concentration, a microemulsion D-phase is present when emulsification starts. The low droplet size and polydispersity and higher stability of these nano-emulsions have been attributed, in addition to the increase in the surface or interfacial activity, to the spontaneous emulsification produced in the microemulsion D-phase.