Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by chromophore confinement into their hollow core. This presentation deals with quaterthiophene derivatives encapsulated into nanotubes displaying different diameter distributions. We show that the supramolecular organizations of the confined chromophores depend on the nanocontainer size. The Raman radial breathing mode frequency is monitored by both the number of confined molecules into a nanotube section and the competition between dye/dye and dye/tube wall interactions. The confinement properties lead also to an exaltation of the infrared absorption response in single-walled carbon nanotubes from dye molecule interactions due to a symmetry breaking, allowing us, thanks to the complementarity of DFT calculations and experimental IR spectra to study interactions between both subsystems. Significant electron transfer from the confined molecules to the nanotubes is also reported from Raman investigations. This charge transfer leads to an important enhancement of the photoluminescence intensity by a factor of nearly five depending on the tube diameter. In addition, close to the molecule resonance, the magnitude of the Raman G-band shifts is modified and the intensity loss is amplified, indicating a photo-induced electron transfer. Results are discussed in the frame of electron-phonon coupling. Thus, confinement species into nanotubes allow moving the Fermi level and consequently to monitor their opto-electronic properties.

Different intracellular delivery systems of bioactive compounds have been developed, including cell-penetrating peptides. Although usually nontoxic and biocompatible, these vectors share some of the general drawbacks of peptides, notably low bioavailability and susceptibility to protease degradation, that limit their use. Herein, the conversion of short peptide sequences into poly-a-amino-g-lactam foldamers that adopt a ribbon-like structure is investigated. This template is used to distribute critical cationic and/or hydrophobic groups on both sides of the backbone, leading to potent short, cell-permeable foldamers with a low positive-charge content. The lead compound showed dramatically improved protease resistance and was able to efficiently deliver a biologically relevant cargo inside cells. This study provided a simple strategy to convert short peptide sequences into efficient protease-resistant cell-penetrating foldamers.

The use of electrochemical template synthesis for the formation of electrochromic composite nickel hydroxide/PVA films with poor inside stress, effective adhesion to substrate and high optical and electrochemical properties is proposed.Influence of the deposition current density and of the amount of PVA on the structure, surface morphology and transparency of the electrodeposit films is investigated. It is thus concluded that the optimal current density is 0.625 mA/cm2 for the pure Ni(OH)2 film whereas the optimal concentration of PVA is 5% weight is. Overall, the electroplated Ni(OH)2/PVA films exhibit an X-ray amorphous structure, due to the Ni(OH)2 particle growth in the nano-size cells of the 3D network of the PVA template. Surface morphology of films, deposited with the template synthesis, is investigated by SEM. The film electrodepositing rate by template synthesis was estimated around the 3.87 μm/h at the current density of the 0.625 mA/cm2. Template incorporating into the nickel hydroxide film has been proved by EDX analysis. Electrochemical and electrochromic properties of films, deposited by electrochemical template synthesis and dried at 20 °C and 90 °C, have been investigated. It was shown that both types of films have high properties (charge/discharge and colorization-bleaching processes). But films, dried at 20 °C, has the best electrochemical properties and larger colorization depth, however the colorization/bleaching process has larger reversibility for the sample dried at 90 °C

The control of structuring and morphology in hybrid solids is a key parameter for the design of functional materials. In particular, it has been shown that structure and morphology could be tuned through sol gel synthesis conditions in bridged silsesquioxanes (BS). As a matter of fact, during sol-gel process, the competition between self-assembing through non covalent interactions between the organic sub-structures and condensation of the inorganic siliceous sub-structure can lead to the formation of crystalline compounds or amorphous materials.In order to go further with the understanding of the control of the nanostructuring in bridged silsequioxane, we designed the organic moieties of the precursors with either 2 symetrical through hydrogen bond and the strength of these hydrogen bonds is studied through vibrational spectroscopies in-situ at low temperature or at high pressure. The results are analyzed and discussed in terms of H bond strength and geometric factors.In the second part of this talk, we will focus on the influence of the central subunit lying between the two urea/thiourea groups_either a long flexible alkyl chain or rigid phenyl group_ on the self-assembling properties through H bonds.

Bridged silsesquioxane nanomaterials exhibit original mechanical properties thanks to the association of non-covalent and covalent interactions. Thanks to in situ high pressure spectroscopic studies, achieved in diamond anvil cells, the mechanical behavior of these materials was followed as a function of pressure. Vibrational studies coupled to ab-initio simulations show that mechanical constrains are absorbed by the modulation of H bond interactions. We thus show that the rigidity yielded by the inorganic polymerization is counterbalanced by the presence of the intermolecular H bond network. In a large range of pressures, these hybrid materials have a reversible behavior, and thus behave as molecular springs. In a second time, we demonstrate that the pressure behavior of these molecular spring is sensitive to the conformation of H bonds (cyclic versus linear) and to the constraints imposed the covalent inorganic network.

An organogelator based on a N,N′-substituted H-bonding perylenebisimide (PBI-C10) self-assembles to form either a green J-type (form I) or a red H-type (form II) aggregate structure. The molecular packing of both polymorphs was determined from a combination of Transmission Electron Microscopy (TEM) (low dose electron diffraction and high resolution), Grazing incidence X-ray diffraction and polarized infrared spectroscopy. To that aim, highly oriented films have been prepared by mechanical rubbing at controlled film temperature and DFT calculations were performed to identify representative vibrational IR bands and their associated polarizations. H-Bonding between amides generates either a rectangular columnar phase (form I) in the dried gel or a hexagonal packing of supramolecular 21/1 helices with a long period of 97 Å (form II) in annealed thin films. In aligned films of form I, polarized FTIR spectroscopy helps determine the orientation of both intermolecular H-bonds and the PBI core with respect to the substrate. In form II, PBI-C10 molecules assemble into pairs to form off-centered 21/1 helices whose helical axis is made of strongly H-bonded amides. TEM investigations show that three 21/1 helices are packed in a frustrated trigonal structure formed by H-bonding. The Form I → Form II transformation implies a redistribution of a single population of strong intra-columnar H-bonds between amides in form I to a mixture of strong and weak H-bonds in the supramolecular helices, the strong H-bonds forming the spine of the helices.

Conversion-type electrode materials show extremely interesting performance in terms of capacity, which is however usually associated with bad Coulombic efficiency. The latter is mainly the consequence of the relentless evolution of solid electrolyte interphase (SEI) formed and/or dissolved during conversion/back-conversion reactions on the continuously reshaping active material surface. The thorough comprehension of the dynamic processes occurring during cycling in a working electrochemical cell, such as solvation/desolvation of ionic species and formation/dissolution of the SEI at the electrode/electrolyte interface, is thus of utmost relevance in the study of electrochemical mechanism and performance of conversion-type electrode materials. Operando Fourier transform infrared (FTIR) spectroscopy, one of the methods of choice for the study of such phenomena, was applied to study the dynamic interfacial properties of NiSb2, a representative intermetallic conversion-type electrode material for Li batteries, during cycling in the presence of a commercial electrolyte based on LiPF6 dissolved in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC). Using a specifically developed in situ ATR-IR electrochemical cell, it was possible to correlate the electrochemical processes to the ratio between solvent molecules associated with Li+ ions and free solvent molecules and thus to follow the dynamic evolution of the concentration of lithium in the electrolyte during cycling.