Behaviour of hybrid inside/out Janus nanotubes at an oil/water interface. A route to self-assembled nanofluidics?

Imogolites are natural aluminosilicate nanotubes that have a diameter of a few nanometers and can be several microns long. These nanotubes have different chemical groups on their internal (Si-OH) and external (Al-OH-Al) surfaces, that can be easily functionalised independently on both surfaces. Here we show that taking advantage of the particular shape and chemistry of imogolite, it is possible to prepare inside/out Janus nanotubes. Two kinds of symmetric Janus nanotubes are prepared: one with an external hydrophilic surface and an internal hydrophobic cavity (imo-CH3) and one with an external hydrophobic surface and a hydrophilic internal cavity (OPA-imo). The behaviour of such inside/out Janus nanotubes at oil/water interfaces is studied. The OPA-imo adsorbs strongly at the oil/water interface and is very efficient in stabilising water-in-oil emulsions through an arrested coalescence mechanism. Imo-CH3 also adsorbs at the oil/water interface. It stabilises oil-in-water emulsions by inducing slow oil-triggered modifications of the viscosity of the continuous phase. The possible transport of small molecules inside the imo-CH3 nanotubes is evidenced, opening up routes towards self-assembled nanofluidics.

Lead and zinc removal from aqueous solutions by aminotriphosphonate-modified converted natural phosphates.

Apatite particles prepared from natural phosphate rock and grafted with nitrilotris(methylene)triphosphonate (NTP) were evaluated for Pb2+ and Zn2+ sorption from aqueous solutions. Sorption capacities as high as 640 mg.g-1 and 300 mg.g-1 could be obtained for the highest organic content (10 wt%). Analysis of the sorption isotherms using Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models revealed that Pb2+ ions have a larger affinity for apatite (sorption energy ≈ 8 kJ.mol-1) than for NTP so that organo-modified surfaces led to a heterogenous adsorption process. In contrast, Zn2+ interacts weakly (sorption energy ≈ 1 kJ.mol-1) and similarly with the mineral surface and the organic moieties following a homogenous sorption process. Such an association of organic metal ligands with reactive apatite surfaces within porous materials appears as a promising strategy to obtain efficient adsorbents at low cost and limited environmental impact.

Plant cell wall inspired xyloglucan/cellulose nanocrystals aerogels produced by freeze-casting.

Cellulose nanocrystals (CNC) and xyloglucan (XG) were used to construct new aerogels inspired by the hierarchical organization of wood tissue, i.e., anisotropic porous cellular solid with pore walls containing oriented and stiff cellulose nanorods embedded in hemicellulose matrix. Aerogels with oriented or disordered pores were prepared by directional and non-directional freeze-casting from colloidal dispersions of XG and CNC at different ratios. XG addition induced a clear improvement of the mechanical properties compared to the CNC aerogel, as indicated by the Young modulus increase from 138 kPa to 610 kPa. The addition of XG changed the pore morphology from lamellar to alveolar and it also decreased the CNC orientation (the Hermans' orientation factor was 0.52 for CNC vs 0.36-0.40 for CNC-XG). The aerogels that contained the highest proportion of XG also retained their structural integrity in water without any chemical modification. These results open the route to biobased water-resistant materials by an easy and green strategy based on polymer adsorption rather than chemical crosslinking.

Adsorption of phenol from an aqueous solution by selected apatite adsorbents: kinetic process and impact of the surface properties.

Batch adsorption experiments were conducted to investigate the removal of phenol from wastewater by addition of three apatites (porous hydroxyapatite (PHAp) and crystalline hydroxyl- (HAp) and fluoroapatite (FAp)). The best performances were obtained with porous hydroxyapatite PHAp, which presented higher adsorption capacities (experimental: 8.2mgg(-1); calculated 9.2mgg(-1)) than HAp and FAp (3-4mgg(-1)). Different models of adsorption were used to describe the kinetics data, to calculate corresponding rate constants and to predict the theoretical capacities of apatite surfaces for phenol adsorption. A mechanism of phenol adsorption associating chemisorption and physisorption processes is presented allowing the discussion of the variations in adsorption behavior between these materials in terms of specific surface area and chemical composition. These data suggest that apatites are promising materials for phenol sorption.

Photoinduced chitosan-PEG hydrogels with long-term antibacterial properties.

Photochemical processes offer the possibility of preparing functional hydrogels under green conditions that are compatible with both synthetic and natural polymers. In this study, chitosan-based poly(ethylene) glycol (PEG) were successfully synthesized under light irradiation in aqueous medium. Kinetic studies under irradiation showed that less than 2 min were necessary to obtain fully cross-linked networks. Thermomechanical analyses and swelling experiments indicated that introduction of chitosan overall weakens the hydrogel network but can create domains of higher thermal stability than the PEG-alone structure. The resulting chitosan-PEG hydrogels demonstrated a tremendous inhibition (100%) of bacterial growth (Escherichia coli and Staphylococcus aureus). After 6 months' ageing, one of the hydrogels preserved a high antifouling activity against Escherichia coli. This interesting result, which could be correlated with the network features, demonstrates the strong potential of these photochemical methods to obtain robust bio-functional materials.

Eosin-mediated synthesis of polymer coatings combining photodynamic inactivation and antimicrobial properties.

Polymer coatings exhibiting photodynamic bacterial inactivation properties have been successfully engineered. Such coatings were obtained by photoinduced crosslinking of a PEG-diacrylate monomer associated with the eosin Y dye which was used as both a radical photoinitiator and an antibacterial agent. A dual curing process was followed by combining compatible and solvent-free polymerization mechanisms, i.e. Aza-Michael reaction and free-radical polymerization in the presence of amines. The kinetics evolution of the photopolymerization process was followed using in situ Fourier transform infrared spectroscopy, allowing for the elucidation of the underlying mechanistic pathways. The influence of eosin Y and amines on the thermal and mechanical properties of the films was evidenced and discussed in terms of crosslinking chemistry. The antibacterial properties of the coatings against two different strains (Escherichia coli and Staphylococcus aureus) were evaluated on short and long terms, revealing that eosin confers both photodynamic inactivation and antimicrobial properties to the films. These coatings are therefore particularly promising for disposable medical devices.

Parameters influencing ciprofloxacin, ofloxacin, amoxicillin and sulfamethoxazole retention by natural and converted calcium phosphates.

The retention of four antibiotics, ciprofloxacin, ofloxacin, amoxicillin and sulfamethoxazole by a natural phosphate rock (francolite) was studied and compared with a converted hydroxyapatite powder. The maximum sorption capacities were found to correlate with the molecular weight of the molecules. The mechanisms of sorption depended mostly on the charge of the antibiotic whereas the kinetics of the process was sensitive to their hydrophobic/hydrophilic character. The two materials showed slightly distinct affinities for the various antibiotics but exhibited similar maximum sorption capacities despite different specific surface areas. This was mainly attributed to the more pronounced hydrophobic character of the francolite phase constituting the natural phosphate. These data enlighten that the retention properties of these mineral phases depend on a complex interplay between the inter-molecular and molecule-solid interactions. These findings are relevant to understand better the contribution of calcium phosphates in the fate and retention of antibiotics in soils.

An aqueous one-pot route to gold/quantum rod heterostructured nanoparticles functionalized with DNA.

We report an original approach exploiting the photoelectrochemical properties of quantum rods and the versatility of Au(I) organometallic chemistry to control DNA surface grafting. This one-pot aqueous approach provides Janus biofunctionalized nanoparticles, the assembly of which should results in the emergence of synergistic properties.

Design of silica-coated microcapsules for bioencapsulation.

Alginate-based microcapsules are coated with silica, providing enhanced mechanical resistance, protein diffusion and allowing enzyme immobilization.

In situ three-dimensional monitoring of collagen fibrillogenesis using SHG microscopy.

We implemented in situ time-lapse Second Harmonic Generation (SHG) microscopy to monitor the three-dimensional (3D) self-assembly of collagen in solution. As a proof of concept, we tuned the kinetics of fibril formation by varying the pH and measured the subsequent exponential increase of fibril volume density in SHG images. We obtained significantly different time constants at pH = 6.5 ± 0.3 and at pH = 7.5 ± 0.3. Moreover, we showed that we could focus on the growth of a single isolated collagen fibril because SHG microscopy is sensitive to well-organized fibrils with diameter below the optical resolution. This work illustrates the potential of SHG microscopy for the rational design and characterization of collagen-based biomaterials.

Pyridine and phenol removal using natural and synthetic apatites as low cost sorbents: influence of porosity and surface interactions.

A natural phosphate rock and two synthetic mesoporous hydroxyapatites were evaluated for the removal of pyridine and phenol from aqueous solutions. Experiments performed by the batch method showed that the sorption process occurs by a first order reaction for both pyridine and phenol. In contrast, the Freundlich model was able to describe sorption isotherms for phenol but not for pyridine. In parallel, the three apatites exhibit similar pyridine sorption capacities whereas phenol loading was in agreement with their respective specific surface area. This was attributed to the strong interaction arising between pyridine and apatite surface that hinders further inter-particular diffusion. This study suggests that, despite its low specific surface area, natural phosphate rock may be used as an efficient sorbent material for specific organic pollutants, with comparable efficiency and lower processing costs than some activated carbons.

Effect of some amino acids and peptides on silicic acid polymerization.

The polymerization of silicic acid in aqueous solutions at different pH was followed by the colorimetric molybdosilicate method. The role of four amino acids (serine, lysine, proline and aspartic acid) and the corresponding homopeptides was studied. All four amino acids behave the same way and favor the condensation of silicic acid. Peptides exhibit a stronger catalytic effect than amino acids but they appear to behave in very different ways depending on the nature of side-groups and pH. Poly-lysine and poly-proline for instance lead to the precipitation of solid phases containing both silica and peptides. The role of these biomolecules on the polymerization of silicic acid is discussed in terms of electrostatic interactions, hydrogen bonds and solubility.

Silica-alginate composites for microencapsulation.

Optimisation of membrane properties of alginate microcapsules is a key factor for the application of microencapsulation techniques to bioartificial organ elaboration. Coacervation and layer-by-layer processes involving additional biopolymers have been extensively studied. Recently, the use of silica as a membrane-forming agent was investigated. This approach was rendered possible by the development of biocompatible routes to silica formation. The composites exhibit enhanced mechanical and thermal stability as well as suitable diffusion properties. Moreover, encapsulated enzymes and cells retain their biological activities. Similarly, silica can be associated to many other biopolymers, opening a promising route for new biocomposites design and biotechnology applications.