ABSTRACT
The self-assembly of condensable amphiphile molecules in water is an attractive approach for the synthesis of mesostructured hybrid materials. In this article, we focus on aminoundecyltriethoxysilane (AUT), a condensable "bola-amphiphile", i.e., an amphiphilic molecule possessing two polar heads on both sides of an aliphatic chain. In the present case, one side is a condensable triethoxysilane, and the other side is an amino group. We report on the self-assembly of AUT in mixtures of water and tetraethoxysilane (TEOS). In situ small-angle X-ray scattering (SAXS) measurements allowed us to follow the evolution of the structure from the liquid state up to the solid material formed upon catalytic polycondensation. Depending on the medium composition, hexagonal or lamellar structures can be observed in the final material. These observations allowed us to propose a model for the self-assembly of AUT in water/TEOS mixtures that we were able to validate by simulations of the SAXS profiles. By taking advantage of the modularity of such a system, it proves possible to prepare in a simple way various structured hybrid materials possessing a high number of available organic functions without using sacrificial surfactant molecules.
ABSTRACT
We report on how the local structure and the diffusional motion change upon increasing the alkyl chain length in 1-alkyl-3-methylimidazolium cation ionic liquids. This study has been performed by combining pulse field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and small angle X-ray scattering (SAXS) experiments. The cationic side chain length varies from ethyl (n = 2) to hexadodecyl (n = 16), while the anion is always bis(trifluoromethanesulfonyl)imide (TFSI). We find that the self-diffusivity of the individual ionic species is correlated to the local structure in the corresponding ionic liquid, namely the nano-segregation into polar and non-polar domains. In agreement with previous results, we observe that for relatively short alkyl chains the cations diffuse faster than the anions; however we also note that this difference becomes less evident for longer alkyl chains and a cross-over is identified at n ≈ 8 with the anions diffusing faster than the cations. Our results indicate that this controversial behavior can be rationalized in terms of different types of cation-cation and anion-anion orderings, as revealed by a detailed analysis of the correlation lengths and their dispersion curves obtained from SAXS data. We also discuss the validity of the Stokes-Einstein relation for these ionic liquids and the evolution of the extrapolated cationic radius that was found to depend non-strictly linearly on n, in agreement with the cation-cation correlation lengths.
ABSTRACT
The dynamics of confined systems is of major concern for both fundamental physics and applications. In this Letter, the dynamics of C60 fullerene molecules inside single walled carbon nanotubes is studied using inelastic neutron scattering. We identify the C60 vibrations and highlight their sensitivity to temperature. Moreover, a clear signature of rotational diffusion of the C60 is evidenced, which persists at lower temperature than in 3D bulk C60. It is discussed in terms of confinement and of reduced dimensionality of the C60 chain.
