NMR spectroscopy has been established as a potent method for the detn. of foldamer structures in soln. However, the NMR techniques could be limited by averaging, so addnl. exptl. techniques are often needed to fully endorse the folding properties of a sequence. The authors have recently demonstrated that oligo-​γ-​peptides composed of 4-​amino(methyl)​-​1,​3-​thiazole-​5-​carboxylic acids (ATCs) adopt an original helical fold stabilized by hydrogen bonds forming C9 pseudocycles. The main objective of the present work is to restudy the folding of ATC oligomer 1 to identify reliable FTIR and NMR structural markers that are of value for tracking the degree of organization of ATC-​based peptides.

A very active branch of materials research based on allotropic carbon nanostructures has recentlyflourished, mainly due to their large potential of applications. Among the most outstanding structures aregraphene and carbon nanotubes which both possess interesting properties at the nanoscale, such as:electronic, mechanical, optical etc... When combined with various nanoparticles (NPs), their potential iseven larger. Exploiting these properties, which are mostly anisotropic, requires to transfer them to themacroscopic world through the preparation of ordered nanostructured composites materials. During theirprocessing, liquid crystal phases present an opportunity to arrange them into macroscopic assemblies ofNPs and nanocarbons with long-range ordering [1]. Nevertheless, achieving high orientational orderparameter and large monodomains remains a challenge. In this work we present some of our approaches toachieve large and well-ordered domains oflyotropic liquid crystals. For example the orderparameter of carbon-nanotubes based materialscan be finely tuned by controlling the length andentanglement of the nanotubes [2] and processesbased on shear are sufficient to easily achieve amacroscopic ordering. For graphene, it is knownthat graphene oxide (GO) flakes easily disperse inwater and spontaneously form liquid crystals athigh concentrations. However, most of their electronic functionalities are lost during the oxidationtreatments. Reduced graphene oxide (RGO) is of greater interest but chemical reduction of GO in watergenerally results in the aggregation of the flakes. We recently showed how to obtain water-based RGOliquid crystals stabilized by surfactant molecules [3]. Structural and thermodynamic characterizationsprovide indirect but statistical information on the dimensions of the graphene flakes. Combined with NPs,these graphene based liquid crystals are also useful to design novel coatings and functional materials.[1] Yuan J. et al. Nat. Commun. 6:8700 doi: 10.1038/ncomms9700 (2015).[2] Zakri, C. et al. Phil. Trans. R. Soc. A., 371, 20120499, pp 1-15 (2013)[3] Zamora-Ledezma, C. et al. J. Phys. Chem. Lett., 3 (17), pp 2425–2430 (2012)

The highly constrained b-amino acid ABOC induces different types of helices in b urea and 1:1 a/b amide oligomers. The latter can adopt 11/9- and 18/16-helical folds depending on the chain length in solution. Short peptides alternating proteinogenic a-amino acids and ABOC in a 2:1 a/b repeat pattern adopted an unprecedented and stable 12/14/14-helix. The structure was established through extensive NMR, molecular dynamics, and IR studies. While the 1:1 a-AA/ABOC helices diverged from the canonical a-helix, the helix formed by the 9-mer 2:1 a/b-peptide allowed the projection of the a-aminoacid side chains in a spatial arrangement according to the a-helix. Such a finding constitutes an important step toward the conception of functional tools that use the ABOC residue as a potent helix inducer for biological applications.

Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by chromophore confinement into their hollow core. For instance, charge transfers are evidenced from Raman data analysis. First, by exciting nanotubes far from the optical absorption of the molecule, the Raman G-band signal exhibits a weak but significant up or downshift depending on the nanotube diameters. This behavior is consistent with a permanent electron transfer to the nanotube in the framework of the renormalization process 1. In addition, close to the molecule resonance, the magnitude of the G-band shift is enhanced for small diameter tubes, evidencing a photo-induced electron transfer. Finally, the Breit-Wigner-Fano lineshape (characteristic of electron-phonon coupling) of the Raman G-band can be strongly reduced for defective metallic nanotubes. After molecule functionalization, this peculiar profile is recovered, suggesting a back donation of electrons to the nanotube. Photoluminescence properties of semiconducting nanotubes are also significantly modified by chromophore confinement. The nanotube emission intensity is amplified after encapsulation. This exaltation depends on the nanotube diameter, and can be related to diameters exactly fitting the molecule size. The origin of the photoluminescence enhancement will be discussed.

Binary c–T phase diagrams of organogelators in solvent are frequently simplified to two domains, gel and sol, even when the melting temperatures display two distinct regimes, an increase with T and a plateau. Herein, the c–T phase diagram of an organogelator in solvent is elucidated by rheology, DSC, optical microscopy, and transmitted light intensity measurements. We evidence a miscibility gap between the organogelator and the solvent above a threshold concentration, cL. In this domain the melting or the formation of the gel becomes a monotectic transformation, which explains why the corresponding temperatures are nonvariant above cL. As shown by further studies by variable temperature FTIR and NMR, different types of H-bonds drive both the liquid–liquid phase separation and the gelation.

Thermo-mechanically durable industrial polymer nanocomposites have great demand as structural components. In this work, highly competent filler design is processed via nano-modified of micronic SiO2/Al2O3 particulate ceramics and studied its influence on the rheology, glass transition temperature, composite microstructure, thermal conductivity, mechanical strength, micro hardness, and tribology properties. Composites were fabricated with different proportions of nano-modified micro-composite fillers in epoxy matrix at as much possible filler loadings. Results revealed that nano-modified SiO2/Al2O3 micro-composite fillers enhanced inter-particle network and offer benefits like homogeneous microstructures and increased thermal conductivity. Epoxy composites attained thermal conductivity of 0.8 W/mK at 46% filler loading. Mechanical strength and bulk hardness were reached to higher values on the incorporation of nano-modified fillers. Tribology study revealed an increased specific wear rate and decreased friction coefficient in such fillers. The study is significant in a way that the design of nano-modified mixed-matrix micro-composite fillers are effective where a high loading is much easier, which is critical for achieving desired thermal and mechanical properties for any engineering applications. Copyright © 2016 John Wiley & Sons, Ltd.