Carlos Rodríguez-Abreu

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.

Microbeads and Hollow Microcapsules Obtained by Self-Assembly of Pickering Magneto-Responsive Cellulose Nanocrystals

Cellulose microbeads can be used as immobilization supports. We report on the design and preparation of magneto-responsive cellulose microbeads and microcapsules by self-assembled shells of cellulose nanocrystals (CNC) carrying magnetic CoFe2O4 nanoparticles, that is, a mixture of isotropic and anisotropic nanomaterials. The magnetic CNCs formed a structured layer, a mesh, consisting of CNCs and magnetic particles bound together on the surface of distinct droplets of hexadecane and styrene dispersed in water. Because of the presence of CNCs the highly crystalline mesh was targeted to provide an improved barrier property of the microbead shell compared to neat polymer shells, while the magnetic particles provided the magnetic response. In situ polymerization of the styrene phase led to the formation of solid microbeads (∼8 μm diameter) consisting of polystyrene (PS) cores encapsulated in the magnetic CNC shells (shell-to-core mass ratio of 4:96). The obtained solid microbeads were ferromagnetic (saturation magnetization of ∼60 emu per gram of the magnetic phase). The magnetic functionality enables easy separation of substances immobilized on the beads. Such a functionality was tested in removal of a dye from water. The microbeads were further utilized to synthesize hollow microcapsules by solubilization of the PS core. The CNC-based, magneto-responsive solid microbeads and hollow microcapsules were characterized by electron microscopy (morphology), X-ray diffraction (phase composition), and magnetometry (magnetic properties). Such hybrid systems can be used in the design of materials and devices for application in colloidal stabilization, concentration, separation, and delivery, among others.

Fabrication of novel silicone capsules with tunable mechanical properties by microfluidic techniques.

A novel approach for the synthesis of silicone capsules using double W/O/W emulsions as templates is introduced. The low viscosity of the silicone precursors enables the use of microfluidic techniques to accurately control the size and morphology of the double emulsion droplets, which after cross-linking result in the desired monodisperse silicone capsules. Their shell thickness can be finely tuned, which in turn allows control over their permeability and mechanical properties; the latter are particularly important in a variety of practical applications where the capsules are subjected to large external forces. The potential of these capsules for controlled release is also demonstrated using a model hydrophilic substance.

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.

Effect of alkyl chain asymmetry on catanionic mixtures of hydrogenated and fluorinated surfactants

In this work we studied and compared the physicochemical properties of the catanionic mixtures cetyltrimethyl-ammonium bromide-sodium dodecanoate, cetyltrimethyl-ammonium bromide-sodium perfluorodacanoate, octyltrimethylammonium bromide-sodium perfluorodacanoate and cetyltrimethyl-ammonium bromide-sodium octanoate by a combination of rheological, transmission electron microscopy (TEM) and polarized optical microscopy measurements. The binary mixtures of the surfactants have been analyzed at different mixed ratios and total concentration of the mixture. Mixtures containing a perfluorinated surfactant are able to form lamellar liquid crystals and stable spontaneous vesicles. Meanwhile, system containing just hydrogenated surfactants form hexagonal phases or they are arranged in elongated aggregates.

Nanocarriers from dicationic bis-imidazolium amphiphiles and their interaction with anionic drugs

Dicationic gemini surfactants based on bis-imidazolium salts with bromide counterions were synthesized and shown to self-assemble into micellar-type structures in aqueous solution. The solubilisation capability of these micelles for anionic drugs (valproate) indicates their great potential as drug nanocarriers. A range of physicochemical techniques including surface tension, fluorescence spectroscopy, small-angle neutron scattering (SANS) and pulsed-gradient spin-echo nuclear magnetic resonance (PGSE-NMR) have been used to determine the nanocarrier (micelle) structure and to quantify the interaction of the drug with the nanocarrier. The insights gained here, structural activity relationships such as hydrophobic dependence of the CMC and drug binding isotherms, will allow for a rational optimization of molecular structure.

Characterization of perylene diimide dye self-assemblies and their use as templates for the synthesis of hybrid and supermicroporous nanotubules.

The self-organizing structures formed by a water-soluble perylene diimide dye (PDI) have been studied by several experimental techniques as potential templates for the preparation of hybrid nanomaterials. The dye forms chromonic-nematic and hexagonal liquid crystals in water. The aggregates in liquid crystals consist of one-molecule-wide stacks. From the changes in the solution proton NMR chemical shifts with concentration, it appears that adjacent molecules are twisted. There is significant broadening of the aromatic resonances at higher concentrations, arising from nonmotionally averaged dipole-dipole coupling between adjacent aromatic hydrogens. This is attributed to slow overall rotation of the aggregates in solution, suggesting that they grow up to several tens of nanometers. Dye aggregates serve as templates for the formation of silica tubules (1-5 μm length, average diameter ≈300 nm), with aligned and very thin (1-2 nm) dye nanostripes embedded in the walls. The silica tubes precipitated from solution are formed by the cooperative interaction between PDI and silica species during the sol-gel reaction. Upon calcination, silica nanotubules with supermicroporous walls are obtained. In comparison with conventional surfactant systems, the use of π-π stacked chromonic aggregates brings new possibilities for the templated fabrication of pores with sizes below the mesoporous range. Materials could find applications in photovoltaics as well as in shape selective catalysis and adsorption.

A supramolecular strategy based on molecular dipole moments for high-quality covalent organic frameworks

A supramolecular strategy based on strong molecular dipole moments is presented to gain access to covalent organic framework structures with high crystallinity and porosity. Antiparallel alignment of the molecules within the pore walls is proposed to lead to reinforced columnar stacking, thus affording a high-quality material. As a proof of principle, a novel pyrene dione building block was prepared and reacted with hexahydroxytriphenylene to form a boronic ester-linked covalent organic framework. We anticipate the strategy presented herein to be valuable for producing highly defined COF structures.

Preparation of Novel Silicone Multicompartment Particles by Multiple Emulsion Templating and Their Use As Encapsulating Systems

Multicompartment poly(dimethylsiloxane) particles were produced for the first time using water-in-oil-in-water (W1/O/W2) emulsions as templates. Multiple silicone W1/O/W2 emulsions were successfully prepared by using silicone precursors with a low viscosity. Several formulation parameters were studied to determine their effect on the properties of emulsions and derived particles. It was observed that the mass fraction of the inner aqueous phase (φ(W1)) and the concentration of both the hydrophobic and hydrophilic surfactants played a crucial role in the morphology and stability of the emulsions. Thus, the derived silicone porous particles also showed different characteristics depending on the emulsion formulation because of the templating effect. At low φ(W1) or high concentrations of the hydrophobic surfactant, particles showed smaller pore sizes as a result of more stable inner droplets. On the other hand, high concentrations of the hydrophobic surfactant resulted in an increase in the size of the derived particles, whereas high concentrations of the hydrophilic surfactant caused the opposite effect. In addition, fluorescein was encapsulated into the hydrophobic particles during the synthesis process and released in a controlled manner. The possibility to encapsulate simultaneously but independently two different hydrophilic components inside the same globule was also tested. On the basis of these results, the obtained silicone porous particles are envisioned to have applications in several advanced fields, for instance, as hydrophobic delivery systems.

Equilibrium and Dynamic Surface Tension Properties of Aqueous Solutions of Sulfonated Cationic‐Nonionic Fluorocarbon Surfactants

The equilibrium and dynamic surface tension properties in aqueous solutions of nonionic and cationic fluorinated surfactants bearing a sulfonated group are reported. Both surfactants show low critical micellar concentration and very low equilibrium surface tension values, but the cationic surfactant is more effective at decreasing surface tension, which is attributed to a small surface area per molecule. In dynamic surface tension measurements both surfactants show an induction time, which is longer for the nonionic surfactant with a higher molecular weight, slower diffusion rates, and higher molecular surface area. The dynamic behavior of surface tension is modeled by a series of exponentials from which a relaxation time for surface tension decay can be estimated. This relaxation time is faster for the cationic surfactant and decreases with both surfactant concentration and temperature. In mixtures of both surfactants, the values of the relaxation time are between those of the pure surfactants, indicating neither synergism nor antagonism.