Achievements, Challenges, and Prospects of Calcium Batteries

This Review flows from past attempts to develop a (rechargeable) battery technology based on Ca via crucial breakthroughs to arrive at a comprehensive discussion of the current challenges at hand. The realization of a rechargeable Ca battery technology primarily requires identification and development of suitable electrodes and electrolytes, which is why we here cover the progress starting from the fundamental electrode/electrolyte requirements, concepts, materials, and compositions employed and finally a critical analysis of the state-of-the-art, allowing us to conclude with the particular roadblocks still existing. As for crucial breakthroughs, reversible plating and stripping of calcium at the metal-anode interface was achieved only recently and for very specific electrolyte formulations. Therefore, while much of the current research aims at finding suitable cathodes to achieve proof-of-concept for a full Ca battery, the spectrum of electrolytes researched is also expanded. Compatibility of cell components is essential, and to ensure this, proper characterization is needed, which requires design of a multitude of reliable experimental setups and sometimes methodology development beyond that of other next generation battery technologies. Finally, we conclude with recommendations for future strategies to make best use of the current advances in materials science combined with computational design, electrochemistry, and battery engineering, all to propel the Ca battery technology to reality and ultimately reach its full potential for energy storage

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

Interfaces and Interphases in Ca and Mg Batteries

The development of high energy density battery technologies based on divalent metals as the negative electrode is very appealing. Ca and Mg are especially interesting choices due to their combination of low standard reduction potential and natural abundance. One particular problem stalling the technological development of these batteries is the low efficiency of plating/stripping at the negative electrode, which relates to several factors that have not yet been looked at systematically; the nature/concentration of the electrolyte, which determines the mass transport of electro-active species (cation complexes) toward the electrode; the possible presence of passivation layers, which may hinder ionic transport and hence limit electrodeposition; and the mechanisms behind the charge transfer leading to nucleation/growth of the metal. Different electrolytes are investigated for Mg and Ca, with the presence/absence of chlorides in the formulation playing a crucial role in the cation desolvation. From a R&D point-of-view, proper characterization alongside modeling is crucial to understand the phenomena determining the mechanisms of the plating/stripping processes. The state-of-the-art is here presented together with a short perspective on the influence of the cation solvation also on the positive electrode and finally an attempt to define guidelines for future research in the field

Covalent grafting onto self-adhesive surfaces based on aryldiazonium salt seed layers

International audienceThe chemistry of aryldiazonium salts has been thoroughly used in recent years to graft in a very simple and robust way ultrathin polyphenylene-like films on a broad range of surfaces. We show here that the same chemistry can be used to obtain self-adhesive surfaces. This target was reached in a simple way by coating various surfaces with chemisorbed organic films containing active aryldiazonium salts. These self-adhesive surfaces are then put into contact with various species (molecules, polymers, nanoparticles, nanotubes, graphene flakes, etc.) that react either spontaneously or under activation with the immobilized aryldiazonium salts. Our self-adhesive surfaces were synthesized following a simple aqueous two-step protocol based on p-phenylenediamine diazotisation. The first diazotisation step results in the robust grafting of thin polyaminophenylene (PAP) layers onto the surface. The second diazotisation step changed the grafted PAP film into a poly-aryldiazonium polymer (PDP) film. The covalent grafting between those self-adhesive surfaces and the target species was achieved by direct contact or by immersion of the self-adhesive surfaces in solution. We present in this preliminary work the grafting of multi-wall carbon nanotubes (MWCNTs), flakes of highly oriented pyrolytic graphite (HOPG), various organic compounds and copper nanoparticles. We also tested these immobilized aryldiazonium salts as electropolymerization initiators for the grafting-to process

Exploring reported genes of microglia RNA-sequencing data:Uses and considerations

The advent of RNA-sequencing techniques has made it possible to generate large, unbiased gene expression datasets of tissues and cell types. Several studies describing gene expression data of microglia from Alzheimer's disease or multiple sclerosis have been published, aiming to generate more insight into the role of microglia in these neurological diseases. Though the raw sequencing data are often deposited in open access databases, the most accessible source of data for scientists is what is reported in published manuscripts. We observed a relatively limited overlap in reported differentially expressed genes between various microglia RNA-sequencing studies from multiple sclerosis or Alzheimer's diseases. It was clear that differences in experimental set up influenced the number of overlapping reported genes. However, even when the experimental set up was very similar, we observed that overlap in reported genes could be low. We identified that papers reporting large numbers of differentially expressed microglial genes generally showed higher overlap with other papers. In addition, though the pathology present within the tissue used for sequencing can greatly influence microglia gene expression, often the pathology present in samples used for sequencing was underreported, leaving it difficult to assess the data. Whereas reanalyzing every raw dataset could reduce the variation that contributes to the observed limited overlap in reported genes, this is not feasible for labs without (access to) bioinformatic expertise. In this study, we thus provide an overview of data present in manuscripts and their supplementary files and how these data can be interpreted

Specific gene correction of the AGXT gene and direct cell reprogramming for the treatment of Primary Hyperoxaluria Type 1

P428 Primary Hyperoxaluria Type 1 (PH1) is an inherited rare metabolic liver disease caused by the deficiency in the alanine: glyoxylate aminotransferase enzyme (AGXT), involved in the glyoxylate metabolism. The only potentially curative treatment is organ transplantation. Thus, the development of new therapeutic approaches for the treatment of these patients appears as a priority.We propose the combination of site-specific gene correction and direct cell reprogramming for the generation of autologous phenotypically healthy induced hepatocytes (iHeps) from skin-derived fibroblast of PH1 patients. For the correction of AGXT mutations, we have designed specific gene editing tools to address gene correction by two different strategies, assisted by CRISPR/Cas9 system. Accurate specific point mutation correction (c.853T-C) has been achieved by homologydirected repair (HDR) with ssODN harbouring wild-type sequence. In the second strategy, an enhanced version ofAGXTcDNAhas been inserted near the transcription start codon of the endogenous gene, constituting an almost universal correction strategy for PH1 mutations. Direct reprogramming of fibroblasts has been conducted by overexpression of hepatic transcription factors and in vitro culture in defined media. In vitro characterization of healthy induced hepatocytes (iHeps) has demonstrated hepatic function of the reprogrammed cells. PH1 patient fibroblasts and , ,

Distinct synovial immunopathology in Behçet disease and psoriatic arthritis

Introduction The aim of the study was to investigate synovial immunopathology differences between early Behcet disease (BD) and psoriatic arthritis (PsA). Methods Needle arthroscopy of an inflamed knee joint was performed in patients with early untreated BD (n = 8) and PsA (n = 9). Synovial fluid (SF) was collected for cytokines, perforin, and granzyme analysis. Eight synovial biopsies per patient were obtained for immunohistochemical analysis of the cellular infiltrate (T cells, natural killer cells, macrophages, B cells, plasma cells, mast cells, and neutrophils), blood vessels as well as expression of perforin and granzyme. The stained slides were evaluated by digital image analysis. Results The global degree of synovial inflammation was similar in the two types of arthritis. In the analysis of the innate immune cell infiltration, there was a striking neutrophilic inflammation in BD synovitis whereas PsA displayed significantly higher numbers of cells positive for c-kit, a marker of mast cells. As for lymphocytes, CD3(+) T cells, but neither CD20(+) B cells nor CD138(+) plasma cells, were significantly increased in BD versus PsA. Further analysis of the T-lymphocyte population showed no clear shift in CD4/CD8 ratio or Th1/Th2/Th17 profile. The SF levels of perforin, an effector molecule of cytotoxic cells, displayed a significant four-to fivefold increase in BD. Conclusions This systematic comparative analysis of early untreated synovitis identifies neutrophils and T lymphocytes as important infiltrating cell populations in BD. Increased levels of perforin in BD suggest the relevance of cytotoxicity in this diseas

Maximising embryo production in endangered sheep breeds: in vitro procedures that complement in vivo techniques

This study investigated the use of previously superovulated ovaries as a source of oocytes, assessing the competence of them for in vitro embryo production. Two superovulatory treatments were performed: equine Chorionic Gonadotrophin (eCG) plus porcine Follicle-Stimulating Hormone (pFSH) in a single dose or the conventional protocol of six decreasing doses of pFSH. Thirty donor ewes of the endangered Ojalada breed were given either the simplified (group S; n=15) or the decreasing-dose (group D; n=15) treatments three times at intervals of ≥50 days. Ovaries were recovered on day 7 after the oestrus following the third treatment, just after embryo flushing, and the oocytes were collected to assess in vitro maturation, fertilisation and development to the blastocyst stage. The two superovulatory treatments did not differ in the mean number of oocytes selected for maturation (7.1±1.2 and 8.5±1.5 per ewe in the D and S groups, respectively). The oocytes recovered from ewes in Group D (87.5%) had a significantly (p<0.05) higher maturation rate than did those recovered from ewes in group S (75%), but no differences were found in fertilisation rate (94% and 94.6% in the D and S groups, respectively); both groups did not differ in their blastocyst rates and the total number of cells in in vitro-produced blastocysts. In the two experimental groups, 1.7 (D) and 1.8 (S) in vitro-produced blastocysts were generated per ewe, which indicate that it is feasible to combine in vivo and in vitro techniques to maximise embryo production in endangered sheep breeds.EEA ChubutFil: Forcada, Fernando. Universidad de Zaragoza. Instituto de Investigación de Ciencias Ambientales de Aragón. Grupo de Biología y Fisiología de la Reproducción; EspañaFil: Buffoni, Andres. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Chubut; ArgentinaFil: Abecia, José Alfonso. Universidad de Zaragoza. Instituto de Investigación de Ciencias Ambientales de Aragón. Grupo de Biología y Fisiología de la Reproducción; EspañaFil: Asenjo, B. Universidad de Valladolid. Escuela Universitaria de Ingenierías Agrarias de Soria; EspañaFil: Palacin, José Ignacio. Universidad de Zaragoza. Instituto de Investigación de Ciencias Ambientales de Aragón. Grupo de Biología y Fisiología de la Reproducción; EspañaFil: Vázquez, M.I. Universidad de Zaragoza. Instituto de Investigación de Ciencias Ambientales de Aragón. Grupo de Biología y Fisiología de la Reproducción; EspañaFil: Rodriguez Castillo, José del Carmen. Benemérita Universidad Autónoma de Puebla. Facultad de Medicina Veterinaria y Zootecnia; MéxicoFil: Sanchez Prieto, L. Universidad de Zaragoza. Instituto de Investigación de Ciencias Ambientales de Aragón. Grupo de Biología y Fisiología de la Reproducción; EspañaFil: Casao, A. Universidad de Zaragoza. Instituto de Investigación de Ciencias Ambientales de Aragón. Grupo de Biología y Fisiología de la Reproducción; Españ