Green syntheses of biobased solvents

The design of bioproducts implies the use of renewable carbon but also the conversion of this carbon through clean processes. This step is often a limiting one if we consider the whole life cycle “from the raw materials to the fate of the products”. We proposed, in this work, to adapt conventional methods to the conversion of a natural raw material, the fusel oil, a co-product generated by ethanol industry to prepare acetates, carbonates and isovalerates. Selected conditions are compared to conventional routes to quantify their ecoefficiency and to check their potential development for the preparation of new biosolvents. In another step, we have calculated the volatile organic compound amount emitted during the production of a new cosmetic formulation using the fusel oil derivatives. This complete but simple example shows how to identify a real competitive alternative to the usual production chains.     

Electrochemical performance of annealed cobalt-benzotriazole/CNTs catalysts towards the oxygen reduction reaction

One of the major limitations yet to the global implementation of polymer electrolyte membrane fuel cells (PEMFCs) is the cathode catalyst. The development of efficient platinum-free catalysts is the key issue to solve the problem of slow kinetics of the oxygen reduction reaction (ORR) and high cost. We report a promising catalyst for ORR prepared through the annealing treatment under inert conditions of the cobalt-benzotriazole (Co-BTA) complex supported on carbon nanotubes (CNTs). The N-rich benzotriazole precursor was chosen based on its ability to complex Co(II) ions and generate under annealing highly reactive radicals able to tune the physicochemical properties of CNTs. X-Ray photoelectron spectroscopy (XPS) was used to follow the surface structure changes and highlight the active electrocatalytic sites towards the ORR. To achieve further evaluation of the catalysts in acidic medium, voltamperometry, rotating disk electrode (RDE), rotating ring-disk electrode (RRDE) and half-cell measurements were performed. The resulting catalysts (Co/N/CNTs) all show catalytic activity towards the ORR, the most active one resulting from annealing at 700 °C. The overall electron transfer number for the catalyzed ORR was determined to be ～3.7 with no change upon the catalyst loading, suggesting that the ORR was dominated by a 4e(-) transfer process. The results indicate a promising alternative cathode catalyst for ORR in fuel cells, although its performance is still lower (overpotential around 110 mV evaluated by RDE and RRDE) than the reference Pt/C catalyst.     

Better management of Western blotting results using professional photo management software

Western blotting is a proven technique essential to a significant proportion of molecular biology projects. However, as results accumulate over the years, managing data can become daunting. Recognizing that the needs of a scientist working with Western blotting results are conceptually the same as those of a professional photographer managing a summer's worth of wedding photos, we report here a new workflow for managing Western blotting results using professional photo management software. The workflow involves (i) scanning all film‐based results; (ii) importing the scans into the software; (iii) processing the scans; (iv) tagging the files with metadata, and (v) creating appropriate “smart‐albums.” Advantages of this system include space savings (both on our hard drives and on our desks), safer archival, quicker access, and easier sharing of the results. In addition, metadata‐based workflows improve cross‐experiment discovery and enable questions like “show me all blots labelled with antibody X” or “show me all experiments featuring protein Y”. As project size and breadth increase, workflows delegating results management to the computer will become more and more important so that scientists can keep focussing on science.     

Role of substrate wettability in the "bubble deposition method" applied to the CeVO4 nanowire films

Homogeneous two-dimensional structures of CeVO(4) nanowires (NWs) deposited on silicon substrates are obtained by means of the bubble deposition method (BDM). Surface wettability (i.e., surface energy) and film ripening (i.e., film thickness) are two major parameters in nanoparticle confinement and deposition. As the presence of surfactant could be detrimental to applications, a washing treatment is developed without CeVO(4) chemical changes or NW film modifications. Careful investigations of the film topography are carried out by atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) is used to check the chemical composition of the film at different stages. Finally, samples made by BDM are compared to those made by dip-coating method, demonstrating the higher efficiency of the BDM in providing large areas of well-organized and dense CeVO(4) monolayer.     

Influence of lipid composition on the thermotropic behavior and size distribution of mixed cationic liposomes

Cationic liposomes are studied mainly as nonviral nucleic acid delivery systems and to a lesser extent as carriers/adjuvants of vaccines and as low-molecular-weight drug carriers. It is well established that the performance and the biological activity of liposomes in general are strongly related to their physicochemical properties. We investigated the thermotropic behavior and the size distribution of mixed cationic liposomes formulated with different percentages of 1,2 dimyristoyl-sn-glycero-3-phosphatidylcholine and one of four cationic amphiphiles characterized by a pyrrolidinium headgroup with the aim of achieving a better understanding of how the molecular structure of the cationic amphiphile and its mole percentage affect the physicochemical properties of the liposomes. Multilamellar vesicles and large unilamellar vesicles were studied by differential scanning calorimetry and turbidity, respectively, to characterize the thermotropic behavior and lipid phase, whereas dynamic light scattering was used to determine size distribution. This study shows that subtle modifications in the cationic amphiphile's molecular structure and in liposome composition may have dramatic effects on the organization of the liposome bilayer and hence on the morphological and physicochemical features of the liposomes, thus being highly relevant to the biological features investigated previously.     

A new route towards redox bistability through the inspection of manganese-porphyrin complexes

The redox and spin versatilities of manganese–porphyrin complexes [Mn^IIP] are examined to construct a redox‐switchable device. The electronic structure of [Mn^IIIP]⁺ was analyzed by using wavefunction‐based calculations (complete active spaces plus single excitations on top of the active spaces, that is, CAS+singles). A non‐negligible σ‐type electron‐transfer configuration is present in the [Mn^IIIP]⁺ S=2 ground state. By contrast, the [Mn^IIP^.]⁺ valence tautomer is a purely π‐type intramolecular charge transfer, thus reflecting an S=3 spin state as a result of the strong ferromagnetic interaction (J=30 meV) between the S=5/2 Mn^II ion and the S=1/2 porphyrin radical cation P^.+. The change of the redox‐sensitive site in the valence tautomer leads to a ‘triangular scheme’ that involves a critical step in which a simultaneous electron transfer and spin change are expected to induce bistability. From the wavefunction inspection, a meso‐substituted porphyrin candidate was designed to support this scenario. The complete active‐space second‐order perturbation theory (CASPT2) adiabatic energy difference between the S=2 and the S=3 spin states was reduced down to 0.15 eV, thereby giving rise to a metastable S=3 state characterized by a 0.10 Å extension of the porphyrin cavity radius. These results not only confirm the rather versatile nature of these inorganic systems but also demonstrate that redox and spin changes are intermingled in this class of compounds and can be used for applied devices.     

First evidence of resistive switching in polycrystalline GaV4S8 thin layers

Recently a new type of reversible and non‐volatile resistive switching was discovered in single crystals of Mott insulators AM₄X₈ (A = Ga, Ge; M = V, Nb, Ta; X = S, Se). Here we report on the first synthesis of thin layers (thicknesses in the 100 to 1000 nm range) of GaV₄S₈ by RF magnetron sputtering process. Energy dispersive spectroscopy, X‐ray diffraction and TEM analyses attest the high quality of polycrystalline GaV₄S₈ thin layers. Electrical measurements demonstrate that deposited GaV₄S₈ thin films exhibit a non‐volatile reversible resistive switching at room temperature with writing/erasing times of ～10 µs and a memory window (R_high – R_low)/ R_low > 33%. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chiral Bis(tetrathiafulvalene)-1,2-cyclohexane-diamides

Chiral bis(TTF) diamides have been obtained in good yields (54–74%) from 1,2-cyclohexane-diamine and the corresponding TTF acyl chlorides. The (R,R)-1 and (S,S)-1 enantiomers have been characterized by circular dichroism and the racemic form by single-crystal X-ray diffraction. The neutral racemic bis(TTF)-diamide shows the formation of a pincer-like framework in the solid state, thanks to the intramolecular S···S interactions. The chemical oxidation in a solution using FeCl₃ provides stable oxidized species, while the electrocrystallization experiments provided radical cation salts. In particular, single-crystal resistivity measurements on the racemic donor with AsF₆⁻ as a counterion demonstrate semiconductor behavior in this material. The DFT and TD-DFT calculations support the structural and chiroptical features of these new chiral TTF donors.     

Development and Validation of a Reversed-Phase HPLC Method with UV Detection for the Determination of L-Dopa in Vicia faba L. Broad Beans

L-Dopa (LD), a substance used medically in the treatment of Parkinson’s disease, is found in several natural products, such as Vicia faba L., also known as broad beans. Due to its low chemical stability, LD analysis in plant matrices requires an appropriate optimization of the chosen analytical method to obtain reliable results. This work proposes an HPLC-UV method, validated according to EURACHEM guidelines as regards linearity, limits of detection and quantification, precision, accuracy, and matrix effect. The LD extraction was studied by evaluating its aqueous stability over 3 months. The best chromatographic conditions were found by systematically testing several C₁₈ stationary phases and acidic mobile phases. In addition, the assessment of the best storage treatment of Vicia faba L. broad beans able to preserve a high LD content was performed. The best LD determination conditions include sun-drying storage, extraction in HCl 0.1 M, chromatographic separation with a Discovery C₁₈ column, 250 × 4.6 mm, 5 µm particle size, and 99% formic acid 0.2% v/v and 1% methanol as the mobile phase. The optimized method proposed here overcomes the problems linked to LD stability and separation, thus contributing to the improvement of its analytical determination.