Commissioning of a multi‐beamline femtoslicing facility at SOLEIL

The investigation of ultrafast dynamics, taking place on the few to sub‐picosecond time scale, is today a very active research area pursued in a variety of scientific domains. With the recent advent of X‐ray free‐electron lasers (XFELs), providing very intense X‐ray pulses of duration as short as a few femtoseconds, this research field has gained further momentum. As a consequence, the demand for access strongly exceeds the capacity of the very few XFEL facilities existing worldwide. This situation motivates the development of alternative sub‐picosecond pulsed X‐ray sources among which femtoslicing facilities at synchrotron radiation storage rings are standing out due to their tunability over an extended photon energy range and their high stability. Following the success of the femtoslicing installations at ALS, BESSY‐II, SLS and UVSOR, SOLEIL decided to implement a femtoslicing facility. Several challenges were faced, including operation at the highest electron beam energy ever, and achievement of slice separation exclusively with the natural dispersion function of the storage ring. SOLEIL's setup also enables, for the first time, delivering sub‐picosecond pulses simultaneously to several beamlines. This last feature enlarges the experimental capabilities of the facility, which covers the soft and hard X‐ray photon energy range. In this paper, the commissioning of this original femtoslicing facility is reported. Furthermore, it is shown that the slicing‐induced THz signal can be used to derive a quantitative estimate for the degree of energy exchange between the femtosecond infrared laser pulse and the circulating electron bunch.     

Small-Angle and Wide-Angle X-Ray Scattering Study of Slow Relaxation Following Phase Transitions of New Bolaamphiphiles Based on N-(12-Betainylamino-Dodecane)-octyl β-D-Glucofuranosiduronamide Chloride

In the present study, we investigated the polymorphism and its time-dependence of a new series of bolaamphiphile molecules based on N-(12-Betainylamino-dodecane)-octyl β-D-Glucofuranosiduronamide Chloride. To obtain six members of this series, the length of the main bridging chain and the lateral chain were varied in order to modify the hydrophilic–lipophilic balance. Another chemical modification was to introduce a diacetylenic unit in the middle of the bridging chain to study the influence of the π–π stacking on the supramolecular organization of these molecules. Dry bolaamphiphiles self-organize in supramolecular structures such as lamellar crystalline structure, L_c; lamellar gel structure, L_β′; lamellar fluid structure, L_α; and lamellar isotropic structure, L. Thermal hysteresis of these structures, following phase transitions, are investigated by small-angle and wide-angle X-ray scattering. Once the thermal cycle is accomplished, the system remains in the kinetically stabilized undercooled high-temperature phase at the temperature of 20°C. Subsequently, the time-dependence of the relaxation to the thermodynamically stable phase is followed, and very slow relaxation for a period on the order of hours or days is observed. The study of the polymorphism and the stability of various phases of this new series of bolaamphiphiles—which are issued from natural primary resources (sugar beet and wheat) and thus interesting for potential application in pharmaceutical, cosmetics, or food industry—was undertaken in this work.     

Mössbauer and X-ray diffraction characterization of Fe60Al40 coatings prepared by thermal spraying

Microstructured (atomized) and nanostructured (milled) Fe₆₀Al₄₀ powders together with their corresponding coatings synthesized by High Velocity Oxy-fuel (HVOF) or Atmospheric Plasma Spray (APS) thermal spraying techniques have been characterized by Mössbauer Spectroscopy (MS) and X-ray Diffraction (XRD). The evolution of the microstructure and the atomic ordering degree in the powders and coatings are discussed at the light of the various processing conditions. The operational correlation between the parameters of the duplex morphology of coatings and the processing parameters is discussed.     

A preliminary study on the development and characterisation of enzymatically grafted P(3HB)-ethyl cellulose based novel composites

In the present study, a novel enzyme-based grafting of poly(3-hydroxybutyrate) [P(3HB)] onto the ethyl cellulose (EC) as a backbone polymer was developed under a mild and ecofriendly environment and laccase was used as a grafting tool. The resulting composites were characterised using various instrumental and imaging techniques. The high intensity of the 3,358 cm^?1 band in the FTIR spectra showed an increase of hydrogen–bonding interactions between P(3HB) and EC at that distinct wavelength region. The morphology was examined by scanning electron microscopy, which showed the well dispersed P(3HB) in the backbone polymer of EC. X-ray diffraction pattern for P(3HB) showed distinct peaks at 2-theta values of 28°, 32°, 34°, 39°, 46°, 57°, 64°, 78° and 84°. In comparison with those of neat P(3HB), the degree of crystallinity for P(3HB)-g-EC decreased. The tensile strength, elongations at break and Young’s modulus of P(3HB)-g-EC reached the highest levels in comparison to the film prepared with pure P(3HB) only, which was too brittle to measure any of the above said characteristics. Results obtained in the present study suggest P(3HB)-g-EC as a potential candidate for various biotechnological applications, such as tissue engineering and packaging.     

Oxidative Stress and Genotoxicity in Melanoma Induction: Impact on Repair Rather Than Formation of DNA Damage?

Keratinocytes and melanocytes, two cutaneous cell types located within the epidermis, are the origin of most skin cancers, namely carcinomas and melanomas. These two types of tumors differ in many ways. First, carcinomas are almost 10 times more frequent than melanomas. In addition, the affected cellular pathways, the mutated genes and the metastatic properties of the tumors are not the same. This review addresses another specificity of melanomas: the role of photo-oxidative stress. UVA efficiently produces reactive oxygen species in melanocytes, which results in more frequent oxidatively generated DNA lesions than in other cell types. The question of the respective contribution of UVB-induced pyrimidine dimers and UVA-mediated oxidatively generated lesions to mutagenesis in melanoma remains open. Recent results based on next-generation sequencing techniques strongly suggest that the mutational signature associated with pyrimidine dimers is overwhelming in melanomas like in skin carcinomas. UVA-induced oxidative stress may yet be indirectly linked to the genotoxic pathways involved in melanoma through its ability to hamper DNA repair activities.     

Chemical assays of end-groups displayed on the surface of poly(ethylene terephthalate) (PET) films and membranes by radiolabeling

Poly(ethylene terephthalate) (PET) films and track-etched microporous membranes naturally display, on their surfaces, reactive chain-ends, i.e. carboxyl and hydroxyl functions. These were assayed by suitable activation (reaction with carbodiimide and tosyl chloride, respectively), followed by coupling with ³H-lysine and liquid scintillation counting of the sample-associated radioactivity. Values ranging between 5 and 30 pmol/cm² (open surface) of labeled end-groups were obtained, depending on the physico-chemical nature of the samples. Basic hydrolysis enriched the PET films with both types of endings (15–25 pmol/cm²). Reduction of films with the NaBH₄-catechol complex in tetrahydrofuran enriched their surfaces with hydroxyl groups. However, this procedure was not readily applicable to the surface modification of membranes; we observed an erosion effect that was confirmed by scanning electron microscope analyses. In contrast with the reduction process, the oxidation with KMnO₄ in 1.2N H₂SO₄ could be easily applied to the modification of either films or membranes; their surfaces were significantly enriched with carboxyl groups (15–50 pmol/cm²). This surface modification strategy has been used for the covalent coupling of adhesive proteins on PET membranes developed as supports for cell cultivation.     

Josephson effect through an isotropic magnetic molecule

We study the Josephson effect through a quantum dot magnet whose spin is isotropic and which is coupled to the dot electron spin via exchange coupling. We calculate the Andreev levels and the supercurrent and examine the intertwined effect of the exchange coupling, Kondo correlation, and superconductivity. The former suppresses Kondo correlations, which triggers phase transitions from the 0 to the pi state, but strong antiferromagnetic coupling restores the 0 state. The asymmetric phase diagram in the exchange coupling suggests that the coupling sign could be determined in experiments.     

Chalcogen Stabilized bis-Hydridoborate Complexes of Cobalt: Analogues of Tetracyclo[4.3.0.02,4.03,5]nonane

Treatment of Li[BH₃ER] (E=Se or Te, R=Ph; E=S, R=CH₂Ph) with [Cp*CoCl]₂ led to the formation of hydridoborate complexes, [{CoCp*Ph}{Cp*Co}{μ-EPh}{μ-κ²-E,H-EBH₃}], 1a and 1 b ( 1 a : E=Se; 1 b : E=Te) and a bis-hydridoborate species [Cp*Co{μ-κ²-Se,H-SeBH₃}]₂, 2 . All the complexes, 1 a , 1 b and 2 are stabilized by β-agostic type interaction in which 1 b represents a novel bimetallic borate complex with a rare B−Te bond. QTAIM analysis furnished direct proof for the existence of a shared and dative B-chalcogen and Co-chalcogen interactions, respectively. In parallel to the formation of the hydridoborate complexes, the reactions also yielded tetracyclic species, [Cp*Co{κ³-E,H,H-E(BH₂)₂-C₅Me₅H₃}], 3 a and 3 b ( 3 a : E=Se and 3 b : E=S), wherein the bridgehead boron atoms are surrounded by one chalcogen, one cobalt and two carbon atoms of a cyclopentane ring. Molecules 3 a and 3 b are best described as the structural mimic of tetracyclo[4.3.0.0^2,4.0^3,5]nonane having identical structure and similar valence electron counts.