Dye encapsulation into host single-walled carbon nanotubes is an elegant way to create hybrid nano-systems with tunable opto-electronic properties. To this aim, different kinds of molecules (either electron donor or acceptor, absorbing either in the blue or the red visible range) are encapsulated into metallic or semiconducting nanotubes displaying different diameters. Up to now, we have mainly studied encapsulated quaterthiophene derivatives (4T), tetracyanoquinodimethane (TCNQ) and phthalocyanine (MPc) molecules. In this work, we discuss the supramolecular organization of dyes inside the nanotube, the optical properties and the charge transfer for some of our hybrid systems. For instance, using Raman spectroscopy, a significant electron transfer is reported with 4T, whose magnitude strongly depends on the nanotube diameter, and on the metallic or semiconducting character. Experiments also suggest a photo-activated electron transfer for small diameter (~9 Å) semiconducting and metallic tubes. Confinement of electron donor (4T) (respectively electron acceptor (TCNQ)) into small diameter tubes leads to a red shift (blue shift) of the optical absorption energy and an increase (decrease) of the photoluminescence intensities, evidenced by the photoluminescence excitation maps.

Dye confinement into carbon nanotube significantly affects the electronic charge density distribution of the final hybrid system. Using the electron-phonon coupling sensitivity of the Raman G-band, we quantify experimentally how charge transfer from thiophene oligomers to single walled carbon nanotube is modulated by the diameter of the nano-container and its metallic or semiconducting character. This charge transfer is shown to restore the electron-phonon coupling into defected metallic nanotubes. For sub-nanometer diameter tube, an electron transfer optically activated is observed when the excitation energy matches the HOMO-LUMO transition of the confined oligothiophene. This electron doping accounts for an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This electron transfer shifts the Fermi level, acting on the photoluminescence efficiency. Therefore, thiophene oligomer encapsulation allows modulating the electronic structure and then the optical properties of the hybrid system.

As three‐dimensional folding is prerequisite to biopolymer activity, complex functions may also be achieved through foldamer science. Because of the diversity of sizes, shapes and folding available with synthetic monomers, foldamer frameworks enable a numerous opportunities for designing new generations of catalysts. We herein demonstrate that heterocyclic γ‐peptide scaffolds represent a versatile platform for enamine catalysis. One central feature was to determine how the catalytic activity and the transfer of chiral information might be under the control of the conformational behaviours of the oligomer.

The dynamic and static properties of the interfacial region between polymer and nanoparticles have wide-ranging consequences on performances of nanomaterials. The thickness and density of the static layer are particularly difficult to assess experimentally due to superimposing nanoparticle interactions. Here, we tune the dispersion of silica nanoparticles in nanocomposites by pre-adsorption of polymer layers in the precursor solutions, and by varying the molecular weight of the matrix chains. Nanocomposite structures ranging from ideal dispersion to repulsive order or various degrees of aggregation are generated and observed by small-angle scattering. Pre-adsorbed chains are found to promote ideal dispersion, before desorption in the late stages of nanocomposite formation. The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-ray and neutron scattering. Only in ideally well-dispersed systems a static interfacial layer of reduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with a form-free density profile optimized using numerical simulations. This interfacial gradient layer is found to be independent of the thickness of the initially adsorbed polymer, but appears to be generated by out-of-equilibrium packing and folding of the pre-adsorbed layer. The impact of annealing is investigated to study the approach of equilibrium, showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure, while the static interfacial layer disappears. This study thus promotes the fundamental understanding of the interplay between effects which are decisive for macroscopic material properties: polymer-mediated interparticle interactions, and particle interfacial effects on surrounding polymer.

Polarized optical microscopy and spectroscopy are progressively becoming key methods for the high-throughput characterization of individual carbon nanotubes (CNTs) and other one-dimensional nanostructures, on substrate and in devices. The optical response of CNTs on substrate in cross polarization experiments is usually limited by the polarization conservation of the optical elements in the experimental setup. We developed a theoretical model taking into account the depolarization by the setup and the optical response of the substrate. We show that proper modelization of the experimental data requires to take into account both noncoherent and coherent light depolarization by the optical elements. We also show how the nanotube signal can be decoupled from the complex reflection factor of the antireflection substrate, which is commonly used to enhance the optical contrast. Finally, we describe an experimental protocol to extract the depolarization parameters and the complex nanotube susceptibility, and how it can improve the chirality assignment of individual carbon nanotubes in complex cases.