Second harmonic scattering reveals different orientational orders inside the hydrophobic cavity of hybrid nanotubes.

Second Harmonic Scattering (SHS) is a suitable technique to investigate the orientational correlations between molecules. This article explores the organization of different dye molecules adsorbed within the hydrophobic porosity of a hybrid organic-inorganic nanotube. Experimental polarization resolved SHS measurements highlight different orientational orders ranking from highly ordered and rigid organizations to disordered assemblies. Microscopic models of assemblies inside the pores are presented and discussed in the context of orientational correlation between the dye molecules. This work shows that the degree of order in the nanotube cavity follows the molecule's affinity within the porosity.

Dried hybrid imogolite nanotubes as solids with a changeable surface area: an insight into textural properties based on the correlation between nitrogen gas adsorption, immersion calorimetry into water, and small angle X-ray scattering.

Powdered samples of three imogolite materials with an inner surface covered with Si-CH3 groups (hybrid IMO-CH3) were prepared by ambient drying at 323 K, freeze drying, and spray drying. Reliable estimates of the intra-tube (SA), inter-tube (SB), and inter-bundle (SC) specific surface areas of these samples were inferred from a model-guided correlation between the results of measurements by small angle X-ray scattering (SAXS), nitrogen gas adsorption, and immersion calorimetry into water. Since the SAXS studies indicated no significant deformations of IMO-CH3 nanotubes upon drying, further studies by gaseous N2 adsorption at 77 K indicated the intra-tube and inter-bundle specific surface areas as being only accessible to this adsorbate. The outer curved surfaces of IMO nanotubes, including the inter-tube surface areas, were evaluated based on the calorimetric measurements of the enthalpy of immersion into water, using the enthalpy of immersion per unit surface area for a modelled curved surface of gibbsite as the conversion factor. Given the uncertainty in the determination of surface areas, the IMO-CH3 samples were found to possess the limiting values of specific surface areas ranging between 1150 and 1480 m2 g-1. In contrast to the two other materials, ambient-dried IMO-CH3 was characterized by the highest value of SC parameter due to the much smaller bundles formed by the constituent imogolite nanotubes. The accessibility of these surface areas, together with the hydrophobic and hydrophilic surface domains, was demonstrated to depend on the nature of the surrounding medium and the size of the adsorbing species.

Hydrophobic dye solubilization via hybrid imogolite nanotubes probed using second harmonic scattering.

This article explores the organization and interactions of Disperse Orange 3 (DO3) hydrophobic dye molecules within hybrid organic-inorganic imogolite nanotubes. In pure water, the DO3 dye molecules self assemble into large insoluble 2D nanosheets whose structure is also explored by molecular dynamics simulations. The dye molecules are however efficiently solubilized in the presence of hybrid imogolite nanotubes. The filling of the internal hydrophobic cavity of the nanotubes is quantified. The organization of the molecules inside the nanotube is probed using the polarization resolved second harmonic scattering (SHS) technique coupled with simulation. At the highest loading, the dyes fill the nanotube with their principal axis parallel to the nanotube walls showing a strong SHS signal due to this encapsulation.

Pickering emulsions stabilized by inside/out Janus nanotubes: Oil triggers an evolving solid interfacial layer.

HYPOTHESIS: In the field of Pickering emulsion, original inside/ouside Janus clays nanoparticles are investigated for their emulsification properties. Imogolite is a tubular nanomineral of the clay family having both inner and outer hydrophilic surfaces. A Janus version of this nanomineral with an inner surface fully covered by methyl groups can be obtained directly by synthesis (Imo-CH3, hybrid imogolite). The hydrophilic/hydrophobic duality of the Janus Imo-CH3 allows the nanotubes to be dispersed in an aqueous suspension and enables emulsification of non-polar compounds due to the hydrophobic inner cavity of the nanotube. EXPERIMENTS: Through the combination of Small Angle X-ray Scattering (SAXS), interfacial observations and rheology, the stabilization mechanism of imo-CH3 in oil-water emulsions has been investigated. FINDINGS: Here, we show that interfacial stabilization of an oil-in-water emulsion is rapidly obtained at a critical Imo-CH3 concentration as low as 0.6 wt%. Below this concentration threshold, no arrested coalescence is observed, and excess oil is expelled from the emulsion through a cascading coalescence mechanism. The stability of the emulsion above the concentration threshold is reinforced by an evolving interfacial solid layer resulting from the aggregation of Imo-CH3 nanotubes that is triggered by the penetration of confined oil front into the continuous phase.

UV-Visible photo-reactivity of permanently polarized inorganic nanotubes coupled to gold nanoparticles.

Hybrid aluminosilicate nanotubes (Imo-CH3) have the ability to trap small organic molecules inside their hydrophobic internal cavity while being dispersed in water owing to their hydrophilic external surface. They also display a curvature-induced polarization of their wall, which favors reduction outside the nanotubes and oxidation inside. Here, we coupled bare plasmonic gold nanoparticles (GNPs) with Imo-CH3 and analyzed for the first time the redox reactivity of these hybrid nano-reactors upon UV illumination. We show that the coupling between GNPs and Imo-CH3 significantly enhances the nanotube photocatalytic activity, with a large part of water reduction occurring directly on the gold surface. The coupling mechanism strongly influences the initial H2 production rate, which can go from ×10 to more than ×90 as compared to bare Imo-CH3 depending on the synthesis route of the GNPs. The present results show that this hybrid photocatalytic nano-reactor benefits from a synergy of polarization and confinement effects that facilitate efficient H2 production.

Size and Strain of Zinc Sulfide Nanoparticles Altered by Interaction with Organic Molecules.

Nanosized zinc sulfides (nano-ZnS) have size-dependent and tunable physical and chemical properties that make them useful for a variety of technological applications. For example, structural changes, especially caused by strain, are pronounced in nano-ZnS < 5 nm in size, the size range typical of incidental nano-ZnS that form in the environment. Previous research has shown how natural organic matter impacts the physical properties of nano-ZnS but was mostly focused on their aggregation state. However, the specific organic molecules and the type of functional groups that are most important for controlling the nano-ZnS size and strain remain unclear. This study examined the size-dependent strain of nano-ZnS synthesized in the presence of serine, cysteine, glutathione, histidine, and acetate. Synchrotron total scattering pair distribution function analysis was used to determine the average crystallite size and strain. Among the different organic molecules tested, those containing a thiol group were shown to affect the particle size and size-induced strain most strongly when added during synthesis but significantly reduced the particle strain when added to as-formed nano-ZnS. The same effects are useful to understand the properties and behavior of natural nano-ZnS formed as products of microbial activity, for example, in reducing environments, or of incidental nano-ZnS formed in organic wastes.

Experimental determination of the curvature-induced intra-wall polarization of inorganic nanotubes.

Inspired by a natural nano-mineral known as imogolite, aluminosilicate inorganic nanotubes are appealing systems for photocatalysis. Here, we studied two types of synthetic imogolites: one is completely hydrophilic (IMO-OH), while the other has a hydrophilic exterior and a hydrophobic interior (IMO-CH3), enabling the encapsulation of organic molecules. We combined UV-Vis diffuse reflectance spectroscopy of imogolite powders and X-ray photoelectron spectroscopy of deposited imogolite films and isolated nanotubes agglomerates to obtain not only the band structure, but also the quantitative intra-wall polarization of both synthetic imogolites for the first time. The potential difference across the imogolite wall was determined to be 0.7 V for IMO-OH and around 0.2 V for IMO-CH3. The high curvature of the nanotubes, together with the thinness of their wall, favors efficient spontaneous charge separation and electron exchange reactions on both the internal and external nanotube surfaces. In addition, the positions of their valence and conduction band edges make them interesting candidates for co-catalysts or doped catalysts for water splitting, among other possible photocatalytic reactions relevant to energy and the environment.

Confined water radiolysis in aluminosilicate nanotubes: the importance of charge separation effects.

Imogolite nanotubes are potentially promising co-photocatalysts because they are predicted to have curvature-induced, efficient electron-hole pair separation. This prediction has however not yet been experimentally proven. Here, we investigated the behavior upon irradiation of these inorganic nanotubes as a function of their water content to understand the fate of the generated electrons and holes. Two types of aluminosilicate nanotubes were studied: one was hydrophilic on its external and internal surfaces (IMO-OH) and the other had a hydrophobic internal cavity due to Si-CH3 bonds (IMO-CH3), with the external surface remaining hydrophilic. Picosecond pulse radiolysis experiments demonstrated that the electrons are efficiently driven outward. For imogolite samples with very few external water molecules (around 1% of the total mass), quasi-free electrons were formed. They were able to attach to a water molecule, generating a water radical anion, which ultimately led to dihydrogen. When more external water molecules were present, solvated electrons, precursors of dihydrogen, were formed. In contrast, holes moved towards the internal surface of the tubes. They mainly led to the formation of dihydrogen and of methane in irradiated IMO-CH3. The attachment of the quasi-free electron to water was a very efficient process and accounted for the high dihydrogen production at low relative humidity values. When the water content increased, electron solvation dominated over attachment to water molecules. Electron solvation led to dihydrogen production, albeit to a lesser extent than quasi-free electrons. Our experiments demonstrated the spontaneous curvature-induced charge separation in these inorganic nanotubes, making them very interesting potential co-photocatalysts.

Dynamics in hydrated inorganic nanotubes studied by neutron scattering: towards nanoreactors in water.

Water dynamics in inorganic nanotubes is studied by neutron scattering technique. Two types of aluminosilicate nanotubes are investigated: one is completely hydrophilic on the external and internal surfaces (IMO-OH) while the second possesses an internal cavity which is hydrophobic due to the replacement of Si-OH bonds by Si-CH3 ones (IMO-CH3), the external surface being still hydrophilic. The samples have internal radii equal to 7.5 and 9.8 Å, respectively. By working under well-defined relative humidity (RH) values, water dynamics in IMO-OH was revealed by quasi-elastic spectra as a function of the filling of the interior of the tubes. When one water monolayer is present on the inner surface of the tube, water molecules can jump between neighboring Si-OH sites on the circumference by 2.7 Å. A self-diffusion is then measured with a value (D = 1.4 × 10-5 cm2 s-1) around half of that in bulk water. When water molecules start filling also the interior of the tubes, a strong confinement effect is observed, with a confinement diameter (6 Å) of the same order of magnitude as the radius of the nanotube (7.5 Å). When IMO-OH is filled with water, the H-bond network is very rigid, and water molecules are immobile on the timescale of the experiment. For IMO-OH and IMO-CH3, motions of the hydroxyl groups are also evidenced. The associated relaxation time is of the order of 0.5 ps and is due to hindered rotations of these groups. In the case of IMO-CH3, quasi-elastic spectra and elastic scans are dominated by the motions of methyl groups, making the effect of the water content on the evolution of the signals negligible. It was however possible to describe torsions of methyl groups, with a corresponding rotational relaxation time of 2.6 ps. The understanding of the peculiar behavior of water inside inorganic nanotubes has implications in research areas such as nanoreactors. In particular, the locking of motions inside IMO-OH when it is filled with water prevents its use under these conditions as a nanoreactor, while the interior of the IMO-CH3 cavity is certainly a favorable place for confined chemical reactions to take place.

Protein-Nanoparticle Interactions: What Are the Protein-Corona Thickness and Organization?

Protein adsorption on a surface is generally evaluated in terms of the evolution of the proteins' structures and functions. However, when the surface is that of a nanoparticle, the protein corona formed around it possesses a particular supramolecular structure that gives a "biological identity" to the new object. Little is known about the actual shape of the protein corona. Here, the protein corona formed by the adsorption of model proteins (myoglobin and hemoglobin) on silica nanoparticles was studied. Small-angle neutron scattering and oxygenation studies were combined to assess both the structural and functional impacts of the adsorption on proteins. Large differences in the oxygenation properties could be found while no significant global shape changes were seen after adsorption. Moreover, the structural study showed that the adsorbed proteins form an organized yet discontinuous monolayer around the nanoparticles.

Partial Transformation of Imogolite by Decylphosphonic Acid Yields an Interface Active Composite Material.

The phosphonic acid moiety is commonly used as an anchoring group for the surface modification of imogolite. However, the impact of the reaction on its structure has never been clearly analyzed before. We study the reaction of imogolite and decylphosphonic acid by combining infrared spectroscopy, X-ray scattering, scanning electron microscopy, transmission electron microscopy, and solid-state nuclear magnetic resonance spectroscopy. Instead of a surface functionalization, we observe the formation of a lamellar phase interconnected with imogolite bundles. Although we find no evidence for grafted imogolite tubes, we observe the expected dispersion characteristics and stabilization of water in toluene emulsions described in the literature. Based on the surface chemistry of imogolite, we propose an explanation for the observed reactivity and link the structural features of the obtained composite material to its dispersibility in toluene and its observed properties at the toluene-water interface.

Exploring Hybrid Imogolite Nanotube Formation via Si/Al Stoichiometry Control.

Hybrid imogolite aluminosilicate nanotubes with methylated internal surface can be obtained by introduction of the corresponding organosilane during their synthesis. However, similarly to pristine imogolite, a number of side products, including proto-imogolite (open-imoLS), allophanes, and aluminum hydroxides, are formed, which ultimately impact on the properties of the dispersions. In order to minimize the proportion of these side products, we have here systematically explored the impact of the initial Si/Al ratio on the content of hybrid imogolite dispersions before and after dialysis. By combining cryo-transmission electron microscopy, inductively coupled plasma mass spectrometry, infrared spectroscopy, and small-angle X-ray scattering, we evidenced that the Si/Al ratio has a large impact on the formation of aluminum hydroxides that can be minimized with a slight excess of Si precursor. However, a large excess of Si is detrimental to the reaction yield leading to an important proportion of proto-imogolite. We propose that the optimal Si/Al ratio of ca. 0.6 can both minimize the proportion of aluminum hydroxides and proto-imogolite. These results suggest that the dynamic and therefore reactive character of imogolite dispersions may have been so far underlooked.

A liquid-crystalline hexagonal columnar phase in highly-dilute suspensions of imogolite nanotubes.

Liquid crystals have found wide applications in many fields ranging from detergents to information displays and they are also increasingly being used in the 'bottom-up' self-assembly approach of material nano-structuration. Moreover, liquid-crystalline organizations are frequently observed by biologists. Here we show that one of the four major lyotropic liquid-crystal phases, the columnar one, is much more stable on dilution than reported so far in literature. Indeed, aqueous suspensions of imogolite nanotubes, at low ionic strength, display the columnar liquid-crystal phase at volume fractions as low as ∼ 0.2%. Consequently, due to its low visco-elasticity, this columnar phase is easily aligned in an alternating current electric field, in contrast with usual columnar liquid-crystal phases. These findings should have important implications for the statistical physics of the suspensions of charged rods and could also be exploited in materials science to prepare ordered nanocomposites and in biophysics to better understand solutions of rod-like biopolymers.

Multipod-like silica/polystyrene clusters.

Multipod-like clusters composed of a silica core and PS satellites are prepared according to a seeded-growth emulsion polymerization of styrene in the presence of size-monodisperse silica particles previously surface-modified with methacryloxymethyltriethoxysilane. Tuning the diameter and concentration of the silica seeds affords homogeneous batches of tetrapods, hexapods, octopods, nonapods and dodecapods with morphology yields as high as 80%. Three-dimensional reconstructions by cryo-electron tomography are presented on large fields for the first time to show the high symmetry and regularity of the clusters demonstrating the good control of the synthesis process. These synthesis experiments are visited again digitally, in order to successfully refine an original simulation model and better understand the correlation between the history of the cluster growth and the final composition of the cluster mixture. Finally, using the model as a predictive tool and varying the extra experimental conditions, e.g. the composition of the surfactant mixture and the styrene concentration, result in trapping other cluster morphologies, such as tripods.

Aging mechanism in model Pickering emulsion.

We study the stability of a model Pickering emulsion system using fluorinated oil and functionalized silica nanoparticles. A special counter-flow microfluidic set-up was used to prepare monodisperse oil droplets in water. The wettability of the monodisperse silica nanoparticles (NPs) could be tuned by surface grafting and the surface coverage of the droplets was controlled using the microfluidic setup. For surface coverage as low as 23%, we observed a regime of Pickering emulsion stability where the surface coverage of emulsion droplets of constant size increases with time, coexisting with an excess of oil phase. Our results demonstrate that the previously observed limited coalescence regime where surface coverage tends to control the average size of the final droplets must be put in a broader perspective.

Nanometer-long Ge-imogolite nanotubes cause sustained lung inflammation and fibrosis in rats.

BACKGROUND: Ge-imogolites are short aluminogermanate tubular nanomaterials with attractive prospected industrial applications. In view of their nano-scale dimensions and high aspect ratio, they should be examined for their potential to cause respiratory toxicity. Here, we evaluated the respiratory biopersistence and lung toxicity of 2 samples of nanometer-long Ge-imogolites. METHODS: Rats were intra-tracheally instilled with single wall (SW, 70 nm length) or double wall (DW, 62 nm length) Ge-imogolites (0.02-2 mg/rat), as well as with crocidolite and the hard metal particles WC-Co, as positive controls. The biopersistence of Ge-imogolites and their localization in the lung were assessed by ICP-MS, X-ray fluorescence, absorption spectroscopy and computed micro-tomography. Acute inflammation and genotoxicity (micronuclei in isolated type II pneumocytes) was assessed 3 d post-exposure; chronic inflammation and fibrosis after 2 m. RESULTS: Cytotoxic and inflammatory responses were shown in bronchoalveolar lavage 3 d after instillation with Ge-imogolites. Sixty days after exposure, a persistent dose-dependent inflammation was still observed. Total lung collagen, reflected by hydroxyproline lung content, was increased after SW and DW Ge-imogolites. Histology revealed lung fibre reorganization and accumulation in granulomas with epithelioid cells and foamy macrophages and thickening of the alveolar walls. Overall, the inflammatory and fibrotic responses induced by SW and DW Ge-imogolites were more severe (on a mass dose basis) than those induced by crocidolite. A persistent fraction of Ge-imogolites (15% of initial dose) was mostly detected as intact structures in rat lungs 2 m after instillation and was localized in fibrotic alveolar areas. In vivo induction of micronuclei was significantly increased 3 d after SW and DW Ge-imogolite instillation at non-inflammatory doses, indicating the contribution of primary genotoxicity. CONCLUSIONS: We showed that nm-long Ge-imogolites persist in the lung and promote genotoxicity, sustained inflammation and fibrosis, indicating that short high aspect ratio nanomaterials should not be considered as innocuous materials. Our data also suggest that Ge-imogolite structure and external surface determine their toxic activity.

Heteroaggregation of titanium dioxide nanoparticles with model natural colloids under environmentally relevant conditions.

The heteroaggregation of engineered nanoparticles (ENPs) with natural colloids (NCs), which are ubiquitous in natural surface waters, is a crucial process affecting the environmental transport and fate of ENPs. Attachment efficiencies for heteroaggregation, α hetero, are required as input parameters in environmental fate models to predict ENP concentrations and contribute to ENP risk assessment. Here, we present a novel method for determining α hetero values by using a combination of laser diffraction measurements and aggregation modeling based on the Smoluchowski equation. Titanium dioxide nanoparticles (TiO2 NPs, 15 nm) were used to demonstrate this new approach together with larger silicon dioxide particles (SiO2, 0.5 µm) representing NCs. Heteroaggregation experiments were performed at different environmentally relevant solution conditions. At pH 5 the TiO2 NPs and the SiO2 particles are of opposite charge, resulting in α hetero values close to 1. At pH 8, where all particles are negatively charged, α hetero was strongly affected by the solution conditions, with α hetero ranging from <0.001 at low ionic strength to 1 at conditions with high NaCl or CaCl2 concentrations. The presence of humic acid stabilized the system against heteroaggregation.