A general method is proposed to produce oriented and highly crystalline conducting polymer layers. It combines the controlled orientation/crystallization of polymer films by high-temperature rubbing with a soft-doping method based on spin-coating a solution of dopants in an orthogonal solvent. Doping rubbed films of regioregular poly(3-alkylthiophene) s and poly(2,5-bis(3-dodecylthiophen- 2-yl) thieno[3,2-b] thiophene) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ) yields highly oriented conducting polymer films that display polarized UV-visible-near-infrared (NIR) absorption, anisotropy in charge transport, and thermoelectric properties. Transmission electron microscopy and polarized UV-vis-NIR spectroscopy help understand and clarify the structure of the films and the doping mechanism. F(4)TCNQ(-) anions are incorporated into the layers of side chains and orient with their long molecular axis perpendicular to the polymer chains. The ordering of dopant molecules depends closely on the length and packing of the alkyl side chains. Increasing the dopant concentration results in a continuous variation of unit cell parameters of the doped phase. The high orientation results in anisotropic charge conductivity (sigma) and thermoelectric properties that are both enhanced in the direction of the polymer chains (sigma = 22 +/- 5 S cm(-1) and S = 60 +/- 2 mu V K-1 ). The method of fabrication of such highly oriented conducting polymer films is versatile and is applicable to a large palette of semiconducting polymers.

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

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.

Double-walled carbon nanotubes (DWNT) are made of two concentric and weakly van der Waals coupled single-walled carbon nanotubes (SWNT). DWNTs are the simplest systems for studying the mechanical and electronic interactions between concentric carbon layers.In this paper we review recent results concerning the intrinsic features of phonons of DWNTs obtained from Raman experiments performed on index-identified DWNTs. The effect of the interlayer distance on the strength of the mechanical and electronic coupling between the layers, and thus on the frequencies of the Raman-active modes, namely the radial breathinglikemodes (RBLMs) and G-modes, are evidenced and discussed.

We present experimental measurements of the features of G band in individual index-identified free-standing double-walled carbon nanotubes. We examine Raman spectra of different electronic configurations of DWNTs, namely: SC@SC, SC@M, M@SC, M@M, and clearly establish that, as in SWNTs, the profile of LO G-mode of each layer is broad (narrow) when the layer is metallic (semiconducting). The dependence of G-modes on thediameter and inter-layer distance in several SC@SC, SC@M, M@SC, M@M index-identified DWNTs is reported. We find, that, independently of the metallic or semiconducting nature of the layers, the frequencies of LO and TO G-mode of the inner and outer layers shift significantly with respect to the frequencies of the same modes in the constituent SWNTs.