Towards standard electrolytes for sodium-ion batteries: physical properties, ion solvation and ion-pairing in alkyl carbonate solvents.

The currently emerging sodium-ion battery technology is in need of an optimized standard organic solvent electrolyte based on solid and directly comparable data. With this aim we have made a systematic study of "simple" electrolyte systems consisting of two sodium salts (NaTFSI and NaPF6) dissolved in three different alkyl carbonate solvents (EC, PC, DMC) within a wide range of salt concentrations and investigated: (i) their more macroscopic physico-chemical properties such as ionic conductivity, viscosity, thermal stability, and (ii) the molecular level properties such as ion-pairing and solvation. From this all electrolytes were found to have useful thermal operational windows and electrochemical stability windows, allowing for large scale energy storage technologies focused on load levelling or (to a less extent) electric vehicles, and ionic conductivities on par with analogous lithium-ion battery electrolytes, giving promise to also be power performant. Furthermore, at the molecular level the NaPF6-based electrolytes are more dissociated than the NaTFSI-based ones because of the higher ionic association strength of TFSI compared to PF6- while two different conformers of DMC participate in the Na+ first solvation shells - a Na+ affected conformational equilibrium and induced polarity of DMC. The non-negligible presence of DMC in the Na+ first solvation shells increases as a function of salt concentration. Overall, these results should both have a general impact on the design of more performant Na-conducting electrolytes and provide useful insight on the very details of the importance of DMC conformers in any cation solvation studies

Holo-like and Druggable Protein Conformations from Enhanced Sampling of Binding Pocket Volume and Shape

Understanding molecular recognition of small molecules by proteins in atomistic detail is key for drug design. Molecular docking is a widely used computational method to mimic ligand–protein association in silico. However, predicting conformational changes occurring in proteins upon ligand binding is still a major challenge. Ensemble docking approaches address this issue by considering a set of different conformations of the protein obtained either experimentally or from computer simulations, e.g., molecular dynamics. However, holo structures prone to host (the correct) ligands are generally poorly sampled by standard molecular dynamics simulations of the apo protein. In order to address this limitation, we introduce a computational approach based on metadynamics simulations called ensemble docking with enhanced sampling of pocket shape (EDES) that allows holo-like conformations of proteins to be generated by exploiting only their apo structures. This is achieved by defining a set of collective variables ..

WRINKLED1 and ACYL‐COA:DIACYLGLYCEROL ACYLTRANSFERASE1 regulate tocochromanol metabolism in Arabidopsis

Photosynthetic organisms such as plants, algae and some cyanobacteria synthesize tocochromanols, a group of compounds that encompasses tocopherols and tocotrienols and that exhibits vitamin E activity in animals. While most vitamin E biosynthetic genes have been identified in plant genomes, regulatory genes controlling tocopherol accumulation are currently unknown.We isolated by forward genetics Arabidopsis enhanced vitamin E (eve) mutants that overaccumulate the classic tocopherols and plastochromanol-8, and a tocochromanol unknown in this species. We mapped eve1 and eve4, and identified the unknown Arabidopsis tocochromanol by using a combination of analytical tools. In addition, we determined its biosynthetic pathway with a series of tocochromanol biosynthetic mutants and transgenic lines.eve1 and eve4 are two seed lipid mutants affecting the WRINKLED1 (WRI1) and ACYL-COA:DIACYLGLYCEROL ACYLTRANSFERASE1 (DGAT1) genes, respectively. The unknown tocochromanol is 11′-12′ γ-tocomonoenol, whose biosynthesis is VITAMIN E 1 (VTE1) - and VTE2-dependent and is initiated by the condensation of homogentisate (HGA) and tetrahydrogeranylgeranyl pyrophosphate.This study identifies the first two regulatory genes, WRI1 and DGAT1, that control the synthesis of all tocochromanol forms in seeds, and shows the existence of a metabolic trade-off between lipid and tocochromanol metabolisms. Moreover, it shows that Arabidopsis possesses a tocomonoenol biosynthetic pathway that competes with tocopherol synthesis

Identification and removal of low-complexity sites in allele-specific analysis of ChIP-seq data

Motivation: High-throughput sequencing technologies enable the genome-wide analysis of the impact of genetic variation on molecular phenotypes at unprecedented resolution. However, although powerful, these technologies can also introduce unexpected artifacts. Results: We investigated the impact of library amplification bias on the identification of allele-specific (AS) molecular events from high-throughput sequencing data derived from chromatin immunoprecipitation assays (ChIP-seq). Putative AS DNA binding activity for RNA polymerase II was determined using ChIP-seq data derived from lymphoblastoid cell lines of two parent-daughter trios. We found that, at high-sequencing depth, many significant AS binding sites suffered from an amplification bias, as evidenced by a larger number of clonal reads representing one of the two alleles. To alleviate this bias, we devised an amplification bias detection strategy, which filters out sites with low read complexity and sites featuring a significant excess of clonal reads. This method will be useful for AS analyses involving ChIP-seq and other functional sequencing assays. Availability: The R package absfilter for library clonality simulations and detection of amplification-biased sites is available from http://updepla1srv1.epfl.ch/waszaks/absfilter Contact: [email protected] or [email protected] Supplementary information: Supplementary data are available at Bioinformatics onlin

Broad Geographic Distribution of Roundscale Spearfish (Tetrapturus georgii) (Teleostei, Istiophoridae) in the Atlantic Revealed by DNA Analysis: Implications for White Marlin and Roundscale Spearfish Management

The recent validation of the roundscale spearfish (Tetrapturus georgii) within the western North Atlantic has introduced new complexities in the management of the overfished white marlin (Kajikia albida) in this region due to historical and contemporary misidentification between the two morphologically similar species. Compounding the management challenge for white marlin, which is currently assessed as a single Atlantic-wide stock, is an unclear picture of the extent of the roundscale spearfish\u27s overall Atlantic distribution. By using genetic tools (mitochondrial DNA ND4L-ND4 locus sequences) for species identification, we confirm that the roundscale spearfish has a much broader distribution than previously known, including the central North Atlantic and much of the western South Atlantic to at least 28°52′S. This much wider Atlantic distribution of the roundscale spearfish sympatric with its morphologically similar congeners, the white marlin and longbill spearfish (Tetrapturus pfluegeri), raises further management complexities: it increases the geographic scale for species misidentification in catch records that form the basis for stock assessments and uncertainty in currently accepted white marlin biological parameters. Additional vigilance in obtaining accurate species identification by improved fishery onboard observer training and incorporation of genetic tools is recommended for informing management of white marlin, longbill spearfish and roundscale spearfish throughout the Atlantic

Fluorescent asymmetric bis-ureas for pyrophosphate recognition in pure water

Three fluorescent asymmetric bis-urea receptors (L1–L3) have been synthesised. The binding properties of L1–L3 towards different anions (fluoride, acetate, hydrogencarbonate, dihydrogen phosphate, and hydrogen pyrophosphate HPpi3?) have been studied by means of 1H-NMR, UV-Vis and fluorescence spectroscopy, single crystal X-ray diffraction, and theoretical calculations. In particular, a remarkable affinity for HPpi3? has been observed in the case L1 (DMSO-d6/0.5% H2O) which also acts as a fluorimetric chemosensor for this anion. Interestingly, when L1 is included in cetyltrimethylammonium (CTAB) micelles, hydrogen pyrophosphate recognition can also be achieved in pure water

Formação de moderadores de CdP: o caso da Educação Permanente dos profssionais do Sistema Único de Saúde

Ações em nível nacional de Educação Permanente em Saúde (EPS), baseadas no conceito de aprendizagem social por meio de Comunidades de Prática (CdPs), estão sendo as respostas inovadoras à necessidade de formação de milhares de profssionais atuantes no SUS. Este trabalho propõe um framework conceitual como subsídio para desenvolver   a   capacitação   de   e-moderadores dessas   comunidades,   o   qual   é apresentado por  meio de um  Ciclo de Moderação em CdPs, composto por quatro etapas. Este framework está sendo utilizado e se mostrado efcaz na formação de aproximadamente 150 moderadores que estão acompanhando comunidades de práticas de aproximadamente 2200 tutores em um curso de aperfeiçoamento semi-presencial, em um projeto de EPS para os profssionais do SUS, de abrangência nacional