CPL-active water-soluble aromatic oligoamide foldamers.

A series of enantiopure water-soluble quinoline-based foldamers were prepared and their optical and chiroptical properties in water were investigated. The new hexameric sequences incorporated either cationic or anionic water-solubilizing chains, and one of the oligomers was additionally functionalized by an electron donating moiety to further modulate the optoelectronic properties. A systematic study revealed strong electronic circular dichroism and circularly-polarized luminescence properties in water, with dissymmetry factors up to 2 × 10-2 in absorption and 5 × 10-3 in emission, regardless of the nature of the solubilizing chains and functions. This study therefore highlights new opportunities for the development of water-soluble and chiroptically-active artificial systems towards chirality-associated applications in aqueous or biological media.

Hyper-Rayleigh Scattering as a New Chiroptical Method: Uncovering the Nonlinear Optical Activity of Aromatic Oligoamide Foldamers.

Molecular helices based on self-organized aromatic oligoamide foldamers have been designed and prepared in their two enantiomeric forms in order to probe their second-order nonlinear chiroptical properties in solution. The quinoline oligoamides were rationally functionalized by electron-donating and electron-withdrawing groups to afford a gradual increase of the electronic polarization of the helical architectures. Their hyper-Rayleigh scattering (HRS) responses in solution were accordingly assessed, using either linearly polarized or circularly polarized incident light. Both methods allowed us to observe nonlinear optical activity that was quantified, for the first time for molecular systems, through circular differential scattering intensity ratios. The hyper-Rayleigh optical activity study reveals important charge-transfer differences within the aromatic oligomers, depending on the helix handedness and on the extent of electronic polarization induced by the appended substituents. The origin of the enantiomeric difference is discussed considering both achiral and chiral contributions. Overall, using aromatic oligoamide foldamers as a chiral model, we demonstrate the capabilities of HRS as a complementary chiroptical method, ideally suited for the analysis of various chiral molecular and supramolecular systems in solution. The reliability and chiral discrimination sensitivity of the method can be further improved through dynamic measurements using standard polarization modulation and heterodyning techniques.

[Cross-cultural experience of knowledge sharing in relation to pain]. / Expérience interculturelle de partage de savoirs autour de la douleur.

Health professionals working in paediatric oncology met in Bamako, Mali, as part of a healthcare partnership between the Gabriel-Touré Hospital in Bamako and the Curie Institute in Paris. Open to dialogue and intercultural encounters, the hospital medical and paramedical teams exchanged views on their practices with a particular focus on pain management.

Material challenges for solar cells in the twenty-first century: directions in emerging technologies.

Photovoltaic generation has stepped up within the last decade from outsider status to one of the important contributors of the ongoing energy transition, with about 1.7% of world electricity provided by solar cells. Progress in materials and production processes has played an important part in this development. Yet, there are many challenges before photovoltaics could provide clean, abundant, and cheap energy. Here, we review this research direction, with a focus on the results obtained within a Japan-French cooperation program, NextPV, working on promising solar cell technologies. The cooperation was focused on efficient photovoltaic devices, such as multijunction, ultrathin, intermediate band, and hot-carrier solar cells, and on printable solar cell materials such as colloidal quantum dots.

Improved photocatalytic activity in RuO2-ZnO nanoparticulate heterostructures due to inhomogeneous space charge effects.

New 2-6 wt% RuO2-ZnO heterojunction nanocatalysts were synthesized by a straightforward two-step procedure. They were composed of a porous network of aggregated 25 nm wurtzite ZnO nanocrystallites modified with RuO2 and showed enhanced light absorption in the visible region due to surface plasmon resonance. In order to investigate the energetic structure of the photocatalyst XPS core line and valence band spectra of in situ in UHV prepared heterointerfaces were compared to results obtained from the particles. The shift of Zn 2p3/2 and O 1s core level spectra was determined to be at least 0.80 ± 0.05 eV for the in situ prepared heterojunction whereas it was found to be 0.40 ± 0.05 and 0.45 ± 0.05 eV, respectively, in the photocatalysts. The different values were ascribed to the reduced size of the particles and the different measurability of band bending at the interface of the heterojunction RuO2-ZnO compared to the nanoparticles. The RuO2/ZnO photocatalysts showed higher photocatalytic activity and recyclability than pure ZnO for the degradation of various dyes under UV light irradiation due to vectorial charge separation of photogenerated electrons and holes resulting from internal electric field, the ruthenium oxide acting as a quasi-metallic contact.

Functionalization of a ruthenium-diacetylide organometallic complex as a next-generation push-pull chromophore.

The design and preparation of an asymmetric ruthenium-diacetylide organometallic complex was successfully achieved to provide an original donor-π-[M]-π-acceptor architecture, in which [M] corresponds to the [Ru(dppe)2] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge-transfer processes occurring upon photoexcitation of the push-pull metal-dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push-pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye-sensitized solar cell devices, showed a good spectral response with a broad incident photon-to-current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications.

New synthetic routes towards soluble and dissymmetric triphenodioxazine dyes designed for dye-sensitized solar cells.

New π-conjugated structures are constantly the subject of research in dyes and pigments industry and electronic organic field. In this context, the triphenodioxazine (TPDO) core has often been used as efficient photostable pigments and once integrated in air stable n-type organic field-effect transistor (OFET). However, little attention has been paid to the TPDO core as soluble materials for optoelectronic devices, possibly due to the harsh synthetic conditions and the insolubility of many compounds. To benefit from the photostability of TPDO in dye-sensitized solar cells (DSCs), an original synthetic pathway has been established to provide soluble and dissymmetric molecules applied to a suitable design for the sensitizers of DSC. The study has been pursued by the theoretical modeling of opto-electronic properties, the optical and electronic characterizations of dyes and elaboration of efficient devices. The discovery of new synthetic pathways opens the way to innovative designs of TPDO for materials used in organic electronics.

Nanostructured SnO2-ZnO heterojunction photocatalysts showing enhanced photocatalytic activity for the degradation of organic dyes.

Nanoporous SnO(2)-ZnO heterojunction nanocatalyst was prepared by a straightforward two-step procedure involving, first, the synthesis of nanosized SnO(2) particles by homogeneous precipitation combined with a hydrothermal treatment and, second, the reaction of the as-prepared SnO(2) particles with zinc acetate followed by calcination at 500 °C. The resulting nanocatalysts were characterized by X-ray diffraction (XRD), FTIR, Raman, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption analyses, transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy. The SnO(2)-ZnO photocatalyst was made of a mesoporous network of aggregated wurtzite ZnO and cassiterite SnO(2) nanocrystallites, the size of which was estimated to be 27 and 4.5 nm, respectively, after calcination. According to UV-visible diffuse reflectance spectroscopy, the evident energy band gap value of the SnO(2)-ZnO photocatalyst was estimated to be 3.23 eV to be compared with those of pure SnO(2), that is, 3.7 eV, and ZnO, that is, 3.2 eV, analogues. The energy band diagram of the SnO(2)-ZnO heterostructure was directly determined by combining XPS and the energy band gap values. The valence band and conduction band offsets were calculated to be 0.70 ± 0.05 eV and 0.20 ± 0.05 eV, respectively, which revealed a type-II band alignment. Moreover, the heterostructure SnO(2)-ZnO photocatalyst showed much higher photocatalytic activities for the degradation of methylene blue than those of individual SnO(2) and ZnO nanomaterials. This behavior was rationalized in terms of better charge separation and the suppression of charge recombination in the SnO(2)-ZnO photocatalyst because of the energy difference between the conduction band edges of SnO(2) and ZnO as evidenced by the band alignment determination. Finally, this mesoporous SnO(2)-ZnO heterojunction nanocatalyst was stable and could be easily recycled several times opening new avenues for potential industrial applications.

Influence of Positional Isomerism on the Chiroptical Properties of Functional Aromatic Oligoamide Foldamers.

A series of functionalized quinoline-based aromatic oligoamide foldamers were prepared in their two enantiomeric forms, comprising an enantiopure terminal camphanyl chiral inducer, which governed the adjacent (P-/M-) helical-handedness. Hierarchical chirality transfer was further investigated in chromophore-appended variants via a range of electronic and vibrational spectroscopic techniques, including circularly polarized luminescence, vibrational circular dichroism and fluorescence. Intense total and polarized photoluminescence (up to Φlum =0.39, glum =1.5×10-3 ) was observed in the visible region from these modular multicomponent architectures and a significant influence of positional isomerism was evidenced. The optimal position of a fluorophore substituent on the quinoline hexamers was determined as being position 2 over position 6, as stronger chiroptical features were systematically observed with the 2-positioned derivatives.

Graphite-type activated carbon from coconut shell: a natural source for eco-friendly non-volatile storage devices.

Carbon from biomass as an active material for supercapacitor electrodes has attracted much interest due to its environmental soundness, abundance, and porous nature. In this context, activated carbon prepared from coconut shells via a simple activation process (water or steam as activation agents) was used as an active material in electrodes for eco-friendly supercapacitors. X-ray diffraction (XRD), Raman spectroscopy, conductivity, scanning electron microscopy (SEM), N2 sorption and thermogravimetry coupled to mass spectrometry (TGA-MS) studies revealed that activated carbon produced by this approach exhibit a graphitic phase, a high surface area, and large pore volume. The energy storage properties of activated carbon electrodes correlate with the morphological and structural properties of the precursor material. In particular, electrodes made of activated carbon exhibiting the largest Brunauer-Emmett-Teller (BET) surface area, i.e. 1998 m2 g-1, showed specific capacitance of 132.3 F g-1 in aqueous electrolyte (1.5 M H2SO4), using expanded graphite sheets as current collector substrates. Remarkably, this sample in a configuration with ionic liquid (1-methyl-1-propy-pyrrolizinium bis(fluorosulfonyl)mide) (MPPyFSI) as electrolyte and a polyethylene separator displayed an outstanding storage capability and energy-power handling capability of 219.4 F g-1 with a specific energy of 92.1 W h kg-1 and power density of 2046.9 W kg-1 at 1 A g-1 and maintains ultra-high values at 30 A g-1 indicating the ability for a broad potential of energy and power related applications. To the best of our knowledge, these values are the highest ever reported for ionic liquid-based supercapacitors with activated carbon obtained from the biomass of coconut shells.

"Chain-like" trimetallic ruthenium complexes with C7 carbon-rich bridges: experimental and theoretical investigations of electronic communication tuning in five distinct oxidation states.

In this work, we report the synthesis and the electronic properties of the unique highly conjugated molecular wires trans-[Cl-(dppe)(2)Ru=C=C=(Ph)C-CH=(CH(3))C-C[triple bond]C-(X)(2)Ru-C=C-C(CH(3))=CH-C(Ph)=C=C=Ru(dppe)(2)Cl](n+) (n = 2, X = dppe ([3a](OTf)(2)) and dppm ([3b](OTf)(2)) with three similar metal centers spanned by two odd-numbered unsaturated C(7) chains providing a 28 A long conjugated path and displaying five well-separated redox states (n = 0-4). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. The electronic and physical properties of the different states were further rationalized with the help of DFT-based calculations. Upon one-electron reduction (n = 1), the single electron is delocalized over the two carbon chains through the central metal atom to an extent driven by the rotations within and between the chains. The second reduction (n = 0) involves the whole carbon-rich conjugated path of the molecule in a spin polarized scheme: one electron is delocalized over each chain, and the two electrons are antiferromagnetically coupled with a coupling on the order of kT. Interestingly, oxidation processes strongly involve both the metal atoms and the bridging ligands. The combined investigations reveal that the mono-oxidized system (n = 3) presents a spin density uniformly distributed between the metal atoms and the carbon atoms of the chains, whereas in the second oxidation state (n = 4) the compounds show a strong antiferromagnetic coupling on the order of 4 kT between the two single electrons localized in two distinct delocalized spin orbitals implying all the carbon atoms of the bridges and the three metal atoms. Thus, for the first time, electronic communication was fully evidenced and tuned in homonuclear trimetallic oligomeric carbon-rich systems in either an oxidation or a reduction process.

Sunlight Selective Photodeposition of CoOx(OH)y and NiOx(OH)y on Truncated Bipyramidal BiVO4 for Highly Efficient Photocatalysis.

Facet-engineered monoclinic scheelite BiVO4 particles decorated with various cocatalysts were successfully synthesized by selective sunlight photodeposition of metal or metal oxy(hydroxide) nanoparticles onto the facets of truncated bipyramidal BiVO4 monoclinic crystals coexposing {010} and {110} facets. X-ray photoelectron spectroscopy, scanning electron microscopy, and scanning Auger microscopy revealed that metallic silver (Ag) and cobalt (oxy)hydroxide (CoOx(OH)y) particles were selectively deposited onto the {010} and {110} facets, respectively, regardless of the cocatalyst amount. By contrast, the nickel (oxy)hydroxide (NiOx(OH)y) photodeposition depends on the nickel precursor amount with an unprecedented selectivity for 0.1 wt % NiOx(OH)y/BiVO4 with a preferential deposition onto the {010} facets and the edges between the {110} facets. Moreover, these noble metal-free heterostructures led to remarkable photocatalytic properties for rhodamine B photodecomposition and sacrificial water oxidation reactions. For instance, 0.2 wt % CoOx(OH)y/BiVO4 led to one of the highest oxygen evolution rates, i.e., 1538 µmol h-1 g-1, ever described which is ten times higher than that found for bare BiVO4. The selective deposition of cobalt (oxy)hydroxide species onto the more electron-deficient facet of truncated bipyramidal monoclinic BiVO4 particles favors photogenerated charge carrier separation and therefore plays a key role for efficient photochemical oxygen evolution.

Aromatic oligoamide foldamers as versatile scaffolds for induced circularly polarized luminescence at adjustable wavelengths.

Quinoline oligoamide foldamers appended with non-chiral fluorophores and derivatized with a camphanyl chiral inducer display strong chiroptical properties at tunable wavelengths as proved by CD and CPL spectroscopies. Induced CPL activity with high luminescence dissymmetry factors was observed in the visible range at wavelengths specific to the fluorophores.

Electronic communication in "chain-like" trimetallic ruthenium complexes with two C7 carbon-rich conjugated bridges.

This paper describes the synthesis and properties of the first homotrinuclear metal complexes with large carbon-rich ligands that provide unique extended conduits for electron mobility.

A self-assembled receptor for the recognition of phosphate and acetate anions in neutral aqueous solution.

The reaction of [(benzene)RuCl(2)](2) with a piperazine-bridged bis(dihydroxypyridine) ligand and LiOH leads to the formation of an expanded helicate, which is able to bind phosphate and acetate in aqueous solution at neutral pH.

Comparison of Fluorinated and Nonfluorinated Lipids in Self-Adjuvanting Delivery Systems for Peptide-Based Vaccines.

Safe immunostimulants (adjuvants) are essential for the development of highly potent peptide-based vaccines. This study examined for the first time whether fluorinated lipids could stimulate humoral immunity in vivo when conjugated to peptide antigen. The impact of fluorination on humoral immunity was tested using a library of peptide-based vaccine candidates against the group A streptococcus (GAS). The fluorinated constructs stimulated similar mouse IgG titers to those elicited by complete Freund's adjuvant (CFA) and were higher than those produced in mice that received the nonfluorinated constructs.

Design and synthesis of novel organometallic dyes for NiO sensitization and photo-electrochemical applications.

Two metallo-organic dyes were synthesized and used for NiO sensitization in view of their photoelectrochemical applications. The new dyes present an original π-conjugated structure containing the [Ru(dppe)2] metal fragment with a highly delocalized allenylidene ligand on one side and a σ-alkynyl ligand bearing an electron-rich group, i.e. a thiophene or triphenylamine unit, and one or two anchoring functions on the other side. The optoelectronic, electrochemical and photoelectrochemical properties of the dyes were systematically investigated. A broad photoresponse was observed with the absorption maximum at 600 nm. The X-ray crystal structure of one precursor was obtained to elucidate the structural conformation of the organometallic complexes and theoretical calculations were performed in order to address the photophysical properties of the new dyes. These photosensitizers were further implemented in NiO-based photocathodes and tested as photocurrent generators under pertinent aqueous conditions in association with [Co(NH3)5Cl]Cl2 as an irreversible electron acceptor. The dye-sensitized photocathodes provided good photocurrent densities (40 to 60 µA cm(-2)) at neutral pH in phosphate buffer and a high stability was observed for the two dyes.

Sterically-controlled regioselective para-substitutions of aniline.

Introduction of sterically demanding 1-isopropyl-2-methylpropyl or triisopropylsilyl groups at the nitrogen of aniline allows high-yielding regioselective para-substitution to be achieved using a lithiation/substitution sequence.

Oligocarbazole-based chromophores for efficient thin-film dye-sensitized solar cells.

Carb your enthusiasm: Carbazole-based sensitizers with high extinction coefficients are synthesized for application in dye-sensitized solar cells (DSCs). The dyes perform efficiently with both iodine and cobalt electrolytes, showing power conversion efficiencies of up to 5.8% on TiO2 films of 15 µm thickness, and retaining 90% of their efficiency in devices with thinner films.

Silica-anchored organotin trichloride: a recyclable and clean organotin catalyst for transesterification reactions.

A new synthetic scheme towards silica-supported organotrichlorotin derivatives has been developed. It involves the synthesis of (11-triethoxysilyl)undecyltricyclohexyltin, followed by sol-gel processing and, subsequently in the formation of the resulting hybrid silica, by electrophilic substitution of the tricyclohexyltin function by the target grafted trichlorotin using tin tetrachloride. HR-MAS (119)Sn and CP-MAS (29)Si NMR combined with N2-sorption and TEM measurements evidenced the formation of a mesoporous organic-inorganic hybrid silica including a functionally pure supported-organotrichlorotin species. This silica-grafted organotrichlorotin displays a satisfactory catalytic activity in the transesterification of ethyl acetate by 1-octanol. The catalyst could be recycled four times without significant loss of activity. Furthermore, tin leaching below 10 ppm evidences the benefits of the proposed strategy to limit tin contamination of the final products.