Electrochemical Cleavage of Alkyl Carbon-Halogen Bonds at Carbon-Metal and Metal-Carbon Substrates: Catalysis and Surface Modification

International audienceThe reaction of ferrocene-tagged primary alkyl iodides (RI) in polar aprotic solvents (dimethylformamide, acetonitrile, and propylene carbonate) in the presence of tetraalkylammonium salts was considered at several kinds of solid electrodes: (i) glassy carbon doped with sub-nanomolar layers of transition metals, graphite, and graphene, and (ii) gold and platinum modified by deposits of natural graphite and graphene. Under such conditions, extensive grafting of alkyl groups onto carbon (as substrate or as modifier) occurred, monitored using the redox response of ferrocene. Details of different modes of C-I bond cleavage at such interfaces are discussed

Gold and gold-graphene used as cathodic interfaces for scission of carbon-halogen bonds. Application to the building of anthraquinone-Au electrodes

International audienceGold (smooth or covered with a thin layer of graphene) is an efficient free-radical scavenger when used as cathode material. This first work points out the immobilization of anthraquinone (AQ) in organic polar solvents containing tetraalkylammonium salts. It appears that Au and graphene, when negatively polarized (E > − 1.0 V vs. Ag/AgCl), may react towards 2-bromomethylantraquinone (AQ-CH2-Br) in different ways: with Au, a fast adsorption followed by one-electron transfer leads to a robust radical modification of the interface, whereas the presence of graphene permits the formation of a benzyl-type radical readily trapped by the graphene layer. Two different redox stable electrodes are thus produced. Additionally, stability of gold-graphene-AQ electrodes could be successfully tested in aqueous buffered solutions

Daniel Forthomme, l’optométriste, le professeur, le chercheur, le directeur et l’ami (1938-2019)

Our friend, Daniel Forthomme, passed away last November 25. This text, dedicated to his memory, list his numerous contributions to optometrists and optometry. Notre ami, Daniel Forthomme, est décédé le 25 novembre dernier. Ce texte, dédié à sa mémoire, énumère ses nombreuses contributions aux optométristes et à l’optométrie

Daniel Forthomme, optometrist, professor, researcher, director and friend (1938-2019)

Daniel Forthomme had a profound influence on many of us and on our profession. Throughout his long career as an optometrist, professor, di-rector of the School of Optometry and of Optométristes Sans Frontières, he adapted to change, always giving his best; hence his remarkable influence on all Quebec op-tometrists and on our profession

Parity Broken Chiral Spin Dynamics in Ba3_3NbFe3_3Si2_2O14_{14}

The spin wave excitations emerging from the chiral helically modulated 120$^{\circ}$ magnetic order in a langasite Ba$_3$NbFe$_3$Si$_2$O$_{14}$ enantiopure crystal were investigated by unpolarized and polarized inelastic neutron scattering. A dynamical fingerprint of the chiral ground state is obtained, singularized by (i) spectral weight asymmetries answerable to the structural chirality and (ii) a full chirality of the spin correlations observed over the whole energy spectrum. The intrinsic chiral nature of the spin waves elementary excitations is shown in absence of macroscopic time reversal symmetry breaking

Optimization of solar power supply systems

My work focuses on the development of approaches to designing solar power systems for the needs of decentralized power supply. It develops an algorithm for determining an optimal structure of power supply system taking into account technical, economic, environmental and social aspects. The case study for the algorithm is the solar power supply system located in decentralized area of the settlement Stepanovka

Helical bunching and symmetry lowering inducing multiferroicity in Fe langasites

International audienceThe chiral Fe-based langasites represent model systems of triangle-based frustrated magnets with a strong potential for multiferroicity. We report neutron scattering measurements for the multichiral Ba3MFe3Si2O14 (M = Nb, Ta) langasites revealing new important features of the magnetic order of these systems: the bunching of the helical modulation along the c-axis and the in-plane distortion of the 120° Fe-spin arrangement. We discuss these subtle features in terms of the microscopic spin Hamiltonian, and provide the link to the magnetically-induced electric polarization observed in these systems. Thus, our findings put the multiferroicity of this attractive family of materials on solid ground

Evaluation of polygenic risk scores for breast and ovarian cancer risk prediction in BRCA1 and BRCA2 mutation carriers

Background: Genome-wide association studies (GWAS) have identified 94 common single-nucleotide polymorphisms (SNPs) associated with breast cancer (BC) risk and 18 associated with ovarian cancer (OC) risk. Several of these are also associated with risk of BC or OC for women who carry a pathogenic mutation in the high-risk BC and OC genes BRCA1 or BRCA2. The combined effects of these variants on BC or OC risk for BRCA1 and BRCA2 mutation carriers have not yet been assessed while their clinical management could benefit from improved personalized risk estimates. Methods: We constructed polygenic risk scores (PRS) using BC and OC susceptibility SNPs identified through population-based GWAS: for BC (overall, estrogen receptor [ER]-positive, and ER-negative) and for OC. Using data from 15 252 female BRCA1 and 8211 BRCA2 carriers, the association of each PRS with BC or OC risk was evaluated using a weighted cohort approach, with time to diagnosis as the outcome and estimation of the hazard ratios (HRs) per standard deviation increase in the PRS. Results: The PRS for ER-negative BC displayed the strongest association with BC risk in BRCA1 carriers (HR = 1.27, 95% confidence interval [CI] = 1.23 to 1.31, P = 8.2 x 10(53)). In BRCA2 carriers, the strongest association with BC risk was seen for the overall BC PRS (HR = 1.22, 95% CI = 1.17 to 1.28, P = 7.2 x 10(-20)). The OC PRS was strongly associated with OC risk for both BRCA1 and BRCA2 carriers. These translate to differences in absolute risks (more than 10% in each case) between the top and bottom deciles of the PRS distribution; for example, the OC risk was 6% by age 80 years for BRCA2 carriers at the 10th percentile of the OC PRS compared with 19% risk for those at the 90th percentile of PRS. Conclusions: BC and OC PRS are predictive of cancer risk in BRCA1 and BRCA2 carriers. Incorporation of the PRS into risk prediction models has promise to better inform decisions on cancer risk management

Numerical Modelling Of The V-J Combinations Of The T Cell Receptor TRA/TRD Locus

T-Cell antigen Receptor (TR) repertoire is generated through rearrangements of V and J genes encoding α and β chains. The quantification and frequency for every V-J combination during ontogeny and development of the immune system remain to be precisely established. We have addressed this issue by building a model able to account for Vα-Jα gene rearrangements during thymus development of mice. So we developed a numerical model on the whole TRA/TRD locus, based on experimental data, to estimate how Vα and Jα genes become accessible to rearrangements. The progressive opening of the locus to V-J gene recombinations is modeled through windows of accessibility of different sizes and with different speeds of progression. Furthermore, the possibility of successive secondary V-J rearrangements was included in the modelling. The model points out some unbalanced V-J associations resulting from a preferential access to gene rearrangements and from a non-uniform partition of the accessibility of the J genes, depending on their location in the locus. The model shows that 3 to 4 successive rearrangements are sufficient to explain the use of all the V and J genes of the locus. Finally, the model provides information on both the kinetics of rearrangements and frequencies of each V-J associations. The model accounts for the essential features of the observed rearrangements on the TRA/TRD locus and may provide a reference for the repertoire of the V-J combinatorial diversity

Identification of a BRCA2-Specific modifier locus at 6p24 related to breast cancer risk

Common genetic variants contribute to the observed variation in breast cancer risk for BRCA2 mutation carriers; those known to date have all been found through population-based genome-wide association studies (GWAS). To comprehensively identify breast cancer risk modifying loci for BRCA2 mutation carriers, we conducted a deep replication of an ongoing GWAS discovery study. Using the ranked P-values of the breast cancer associations with the imputed genotype of 1.4 M SNPs, 19,029 SNPs were selected and designed for inclusion on a custom Illumina array that included a total of 211,155 SNPs as part of a multi-consortial project. DNA samples from 3,881 breast cancer affected and 4,330 unaffected BRCA2 mutation carriers from 47 studies belonging to the Consortium of Investigators of Modifiers of BRCA1/2 were genotyped and available for analysis. We replicated previously reported breast cancer susceptibility alleles in these BRCA2 mutation carriers and for several regions (including FGFR2, MAP3K1, CDKN2A/B, and PTHLH) identified SNPs that have stronger evidence of association than those previously published. We also identified a novel susceptibility allele at 6p24 that was inversely associated with risk in BRCA2 mutation carriers (rs9348512; per allele HR = 0.85, 95% CI 0.80-0.90, P = 3.9×10−8). This SNP was not associated with breast cancer risk either in the general population or in BRCA1 mutation carriers. The locus lies within a region containing TFAP2A, which encodes a transcriptional activation protein that interacts with several tumor suppressor genes. This report identifies the first breast cancer risk locus specific to a BRCA2 mutation background. This comprehensive update of novel and previously reported breast cancer susceptibility loci contributes to the establishment of a panel of SNPs that modify breast cancer risk in BRCA2 mutation carriers. This panel may have clinical utility for women with BRCA2 mutations weighing options for medical prevention of breast cancer