Colloidal Self-Assembly of Silver Nanoparticle Clusters for Optical Metasurfaces.

Optical metasurfaces are two-dimensional assemblies of nanoscale optical resonators and could constitute the next generation of ultrathin optical components. The development of methods to manufacture these nanostructures on a large scale is still a challenge, while most performance demonstrations were obtained with lithographically fabricated metasurfaces that are restricted to small scales. Self-assembly fabrication routes are promising alternatives and have been used to produce original nanoresonators. Reports of self-assembled metasurface fabrication, however, are still scarce. Here, we show that an emulsion-based formulation approach can be used both for the fabrication of complex colloidal resonators, presenting a strong interaction with light, in particular due to simultaneous magnetic and electric modes of resonance, and for their deposition in homogeneous films. This fabrication technique involves emulsification of an aqueous suspension of silver nanoparticles in an oil phase, followed by controlled drying of the emulsion, and produces silver colloidal clusters. We show that the drying process can be controlled in a liquid emulsion, producing a metafluid, as well as in a sedimented emulsion, producing a metasurface. The structural control of the synthesized colloidal clusters is demonstrated with electron microscopy and X-ray scattering techniques. Using a polarization-resolved multiangle light scattering setup in the visible wavelength range, we conduct a comprehensive angular and spectroscopic study of the optical resonant scattering of the nanoresonators in a metafluid and show that they present strong optical magnetic resonances and directional forward-scattering patterns, with scattering efficiencies of up to 4. The metasurfaces consist of homogeneous films, of variable surface density, of colloidal clusters that have the same extinction properties on the surface and in the fluid. This experimental approach allows for large-scale production of metasurfaces.

TiO2-SiO2 Self-Standing Materials bearing Hierarchical Porosity: MUB-200(x) Series toward 3D-Efficient VOC Photoabatement Properties.

Three-dimensional photoactive self-standing porous materials have been synthesized through the integration of soft chemistry and colloids (emulsions, lyotrope mesophases, and P25 titania nanoparticles). Final multiscale porous ceramics bear 700-1000 m2 g-1 of micromesoporosity depending on the P25 nanoparticle contents. The applied thermal treatment does not affect the P25 anatase/rutile allotropic phase ratio. Photonic investigations correlated with the foams' morphologies suggest that the larger amount of TiO2 that is introduced, the larger the walls' density and the smaller the mean size of the void macroscopic diameters, with both effects inducing a reduction of the photon transport mean free path (lt) with the P25 content increase. A light penetration depth in the range of 6 mm is reached, thus depicting real 3D photonic scavenger behavior. The 3D photocatalytic properties of the MUB-200(x) series, studied in a dynamic "flow-through" configuration, show that the highest photoactivity (concentration of acetone ablated and concentration of CO2 formed) is obtained with the highest monolith height (volume) while providing an average of 75% mineralization. These experimental results validate the fact that these materials, bearing 3D photoactivity, are paving the path for air purification operating with self-standing porous monolith-type materials, which are much easier to handle than powders. As such, the photocatalytic systems can now be advantageously miniaturized, thereby offering indoor air treatment within vehicles/homes while drastically limiting the associated encumbrance. This volumetric counterintuitive acting mode for light-induced reactions may find other relevant advanced applications for photoinduced water splitting, solar fuel, and dye-sensitized solar cells while both optimizing photon scavenging and opening the path for the miniaturization of the processes where encumbrance or a foot-print penalty would be advantageously circumvented.

Biosourced Polymeric Emulsifiers for Miniemulsion Copolymerization of Myrcene and Styrene: Toward Biobased Waterborne Latex as Pickering Emulsion Stabilizer.

Biobased waterborne latexes were synthesized by miniemulsion radical copolymerization of a biosourced ß-myrcene (My) terpenic monomer and styrene (S). Biobased amphiphilic copolymers were designed to act as stabilizers of the initial monomer droplets and the polymer colloids dispersed in the water phase. Two types of hydrophilic polymer backbones were hydrophobically modified by terpene molecules to synthesize two series of amphiphilic copolymers with various degrees of substitution. The first series consists of poly(acrylic acid) modified with tetrahydrogeraniol moieties (PAA-g-THG) and the second series is based on the polysaccharide carboxymethylpullulan amino-functionalized with dihydromyrcenol moieties (CMP-g-(NH-DHM)). The produced waterborne latexes with diameters between 160 and 300 nm and were composed of polymers with varying glass transition temperatures (Tg, PMy = -60 °C, Tg, P(My-co-S) = -14 °C, Tg, PS = 105 °C) depending on the molar fraction of biobased ß-myrcene (fMy,0 = 0, 0.43, or 1). The latexes successfully stabilized dodecane-in-water and water-in-dodecane emulsions for months at all compositions. The waterborne latexes composed of low Tg poly(ß-myrcene) caused interesting different behavior during drying of the emulsions compared to polystyrene latexes.

Stabilization of all-aqueous droplets by interfacial self-assembly of fatty acids bilayers.

All-aqueous microdroplets produced by liquid-liquid phase separation have emerged as promising models of artificial cells, and offer new approaches for the solvent-free encapsulation of fragile solutes. Yet, the lack of a membrane on such droplets makes them intrinsically unstable against coarsening, and precludes a fine control over chemical localization, as solutes can freely diffuse through the interface. Herein, we report the construction of stable and impermeable water-in-water emulsions via the interfacial self-assembly of mixed sodium oleate/1-decanol bilayers on dextran-rich droplets produced by segregative liquid-liquid phase separation with poly(ethylene glycol). Lipids spontaneously self-assemble as multilamellar structures at the surface of the droplets as revealed by freeze-fracture transmission electron microscopy and small-angle X-ray scattering. We further demonstrate that the lipid-based membrane is impermeable to oligonucleotides and proteins, but also to a low molecular weight dye, so that a strict chemical encapsulation can be achieved by spontaneous partitioning within the droplets before membrane self-assembly. Taken together, our results highlight the ease of production of fatty acid-stabilized all-aqueous emulsions droplets able to encapsulate a range of solutes without the need of oil or organic solvents, paving the way to the construction of robust membrane-bounded, polymer-rich artificial cells.

Design of Binary Nb2O5-SiO2 Self-Standing Monoliths Bearing Hierarchical Porosity and Their Efficient Friedel-Crafts Alkylation/Acylation Catalytic Properties.

Alkylation of aromatic hydrocarbons is among the most industrially important reactions, employing acid catalysts such as AlCl3, H2SO4, HF, or H3PO4. However, these catalysts present severe drawbacks, such as low selectivity and high corrosiveness. Taking advantage of the intrinsic high acid strength and Lewis and Brønsted acidity of niobium oxide, we have designed the first series of Nb2O5-SiO2(HIPE) monolithic catalysts bearing multiscale porosity through the integration of a sol-gel process and the physical chemistry of complex fluids. The MUB-105 series offers efficient solvent-free heterogeneous catalysis toward Friedel-Crafts monoalkylation and -acylation reactions, where 100% conversion has been reached at 140 °C while cycling. Alkylation reactions employing the MUB-105(1) catalyst have a maximum turnover number (TON) of 104 and a turnover frequency (TOF) of 9 h-1, whereas for acylation, MUB-105(1) and MUB-105(2) yield maximum TON and TOF values of 107 and 11 h-1, respectively. Moreover, the catalysts are selective, producing equal amounts of ortho- and para-substituted alkylated products and greater than 90% of the para-substituted acylated product. The highest catalytic efficiencies are obtained for the MUB-105(1) catalyst, bearing the smallest Nb2O5 particle sizes, lowest Nb2O5 content, and the highest amorphous character. The catalysts presented here are in a monolithic self-standing state, offering easy handling, reusability, and separation from the final products.

The Role of Amylogenic Fiber Aggregation on the Elasticity of a Lipid Membrane.

This work presents a systematic study of the swelling behavior of a lecithin lamellar phase incorporating different amounts of the short peptide sequence diphenylalanine (FF). Small- and wide-angle X-ray scattering assays provide relevant information about the structure and elasticity of the lamellar stacking. These data show that important changes occur at the interface of the lipid membrane dependent not only on the peptide content but also on the hydration of the lamellar structure. Multilamellar-to-unilamellar transitions, previously observed for an increasing number of peptides, are now observed to be dependent on the hydration of the lamellar phase. Wide-angle X-ray scattering and electron microscopy observations (TEM) provide experimental evidence of peptide aggregation into long amylogenic fibers. We argue that aggregates that partition in water may become large enough to destabilize the lamellar structure. It is also shown that, for a given peptide concentration, the lamellar structure can be rendered more flexible or more rigid, by tuning the hydration.

Ex vivo transdermal absorption of a liposome formulation of diclofenac.

Topical formulations of non-steroidal anti-inflammatory drugs are often used to provide effective local drug concentration while limiting systemic exposure and associated adverse events. Formulation composition has great influence on the rate of transdermal drug transport through human skin. This study was performed to compare the ex vivo transdermal transport of diclofenac from three topical formulations, a 1% liposomal gel formulation of diclofenac sodium and two emulsion gel formulations, 1.16% and 2.32% diclofenac diethylamine (equivalent to 1% and 2% diclofenac sodium). Human skin was obtained during unrelated surgical procedures and frozen at -20 °C until use. Three skin specimens were thawed, prepared for testing, and placed in a Franz cell with the stratum corneum facing the donor compartment. About 200 µl of each formulation was placed on the skin, and the receptor compartment fluid (phosphate buffered saline, pH 7.4, 32 °C) was sampled over the next 48 h. Diclofenac concentration was measured with a validated HPLC method. The transdermal permeability coefficient for the liposome 1% gel was 69.3 ± 14.4 10-8 cm•s-1, compared with 34.9 ± 9.1 10-8 cm•s-1 (P = 0.001) and 47.1±9.5 10-8 cm•s-1 (P = 0.005) for the emulsion gel 1.16% and emulsion gel 2.32%, respectively. A statistically significant difference between transdermal transport of diclofenac from the liposome gel 1% and the emulsion gel 1.16% was evident after 9 h, a clinically relevant result because these products are typically applied 2 to 4 times daily. Based on these observations, liposome gel 1% formulation of diclofenac may have a clinical advantage compared with the emulsion gel 1.16% formulation.

Carbon nanotube fiber mats for microbial fuel cell electrodes.

Novel carbon nanotube based electrodes of microbial fuel cells (MFC) have been developed. MFC is a promising technology for the wastewater treatment and the production of electrical energy from redox reactions of natural substrates. Performances of such bio-electrochemical systems depend critically on the structure and properties of the electrodes. The presently developed materials are made by weaving fibers solely comprised of carbon nanotubes. They exhibit a large scale porosity controlled by the weaving process. This porosity allows an easy colonization by electroactive bacteria. In addition, the fibers display a nanostructuration that promotes excellent growth and adhesion of the bacteria at the surface of the electrodes. This unique combination of large scale porosity and nanostructuration allows the present electrodes to perform better than carbon reference. When used as anode in a bioelectrochemical reactor in presence of Geobacter sulfurreducens bacteria, the present electrodes show a maximal current density of about 7.5mA/cm2.

Development of pharmaceutical clear gel based on Peceol®, lecithin, ethanol and water: Physicochemical characterization and stability study.

The phase behavior of the four-components Peceol®/lecithin/ethanol/water system has been studied in a part of the phase diagram poor in water and varying the lecithin/Peceol® ratio. Using several complementary techniques such as Karl Fischer titration, rheology, polarized microscopy and SAXS measurements several nanostructures of the complex systems were identified. W/O microemulsion (L2) as well as an inverted hexagonal (H2) liquid-crystal phase were studied. The analysis of the different phase transitions allows us to understand the effect of lecithin on the water solubilization efficiency of this clear gel and to show its pharmaceutical interest among lecithin organogels.

Polymorphism of natural fatty acid liquid crystalline phases.

We study the phase behavior in water of a mixture of natural long chain fatty acids (FAM) in association with ethylenediamine (EDA) and report a rich polymorphism depending on the composition. At a fixed EDA/FAM molar ratio, we observe upon dilution a succession of organized phases going from a lamellar phase to a hexagonal phase and, finally, to cylindrical micelles. The phase structure is established using polarizing microscopy, SAXS, and SANS. Interestingly, in the lamellar phase domain, we observe the presence of defects upon dilution, which SAXS shows to correspond to intrabilayer correlations. NMR and FF-TEM techniques suggest that these defects are related to an increase in the spontaneous curvature of the molecule monolayers in the lamellae. ATR-FTIR spectroscopy was also used to investigate the degree of ionization within these assemblies. The successive morphological transitions are discussed with regards to possible molecular mechanisms, in which the interaction between the acid surfactant and the amine counterion plays the leading role.

Ion extraction mechanism studied in a lyotropic lamellar phase.

In this paper we used a surfactant-stabilized lyotropic lamellar model system to study the interfacial behavior of an ion-extracting agent: N(1),N(3) dimethyl-N(1),N(3)-dibutyl-2-tetradecylmalonamide (DMDBTDMA). An analysis of small-angle X-ray scattering (SAXS) and polarized attenuated total reflectance-Fourier transform infrared (ATR-FTIR) data enabled us to describe the distribution of the malonamide extractant within the bilayers and its complexation state at the equilibrium. The lamellar phase was diluted with salt water containing varying amounts of complexing salt, and each structural state measured was described using a thermodynamic model based on three elementary equilibria: (i) partition of the extractant polar heads between the core and the polar shell of the bilayers, (ii) the complexation of ions by extractants at the bilayers surfaces, and (iii) the partition of bonded extractants between the core and interfaces of bilayers. This model enabled us to compare the energy cost of each step.

Freeze-fracture TEM imaging of robust order in swollen phases of amphiphilic diblock copolymers.

We report on the structures exhibited by two different diblock poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) copolymers in water, a selective solvent. Using a combination of X-ray scattering and freeze fracture-transmission electron microscopy (FF-TEM), we show that these structures can be widely swollen while retaining their initial morphology and a high degree of long-range order. The analysis of the FF-TEM pictures also evidences the presence of water crystallites of regular size and shape within the confined water domains. We relate the growth of these crystallites to the high local ionic strength of the water swelling the PAA brushes. Moreover, the confinement of the crystallites growth shows that the swollen phases have a very robust structure, potentially useful for confining colloidal particles.

Self-assembly of silica particles in a nonionic surfactant hexagonal mesophase.

We investigate the process of self-assembly, and the resultant structures in composites of silica particles with a hexagonal mesophase of a nonionic surfactant and water. We report a systematic transition in behavior when the particle size is increased relative to the characteristic mesophase spacing. Water dispersible cage-like silsesquioxanes that are molecular analogues of silica particles and are smaller than the mesophase spacing swell the space between the surfactant cylinders. Silica particles comparable to the characteristic hexagonal spacing partition into the hexagonal phase and into strandlike particulate aggregates. Even larger particles phase separate from the hexagonal phase to form particulate strands that organize with a mesh size comparable to the wavelength of visible light. This self-assembly is reversible and the particles disperse by breaking up the aggregates on heating the composite into the isotropic phase. On cooling from the isotropic phase into the hexagonal, the particles are expelled from the growing hexagonal domains and finally impinge to form strandlike aggregates. Unusually, the isotropization temperature is increased in the composites as the particles nucleate the formation of the hexagonal phase.