Conditioning-Free Mg Electrolyte by the Minor Addition of Mg(HMDS)₂

Mg-based batteries are an attractive next-generation energy storage chemistry due to the high natural abundance and inexpensive cost of Mg, along with the high theoretical energy density compared to that of conventional Li-ion chemistry. The greater energy density is predicated on a Mg metal anode, and pathways to achieving reversible Mg electrodeposition and stripping are reliant on the development of Mg electrolytes. Although Mg electrolyte chemistry has advanced significantly from the reactive Grignards of the 1920s to the carboranes of this decade, there remains significant challenges in correlating the Mg metal anode electrochemistry with the composition of the electrolyte salts as a result of the complicated interface of Mg metal and the electrolyte. To probe the effect of the interface on Mg electrodeposition, we turn to an electrolyte with a known solution-phase composition: the magnesium aluminum chloride complex (MACC) electrolyte. The MACC electrolyte requires electrolytic conditioning to support reversible Mg electrodeposition and stripping. Here, we show that a small concentration (2–5 mM) of Mg(HMDS)₂ with respect to the MACC electrolyte salts suppresses Al³⁺ deposition and promotes reversible Mg electrodeposition and stripping in the first cycle. The significant effect of a small concentration of additive is attributed to changes to the electrode interface. The impact of the Mg interface on the observed electrochemical performance is discussed

Effect of the Electrolyte Solvent on Redox Processes in Mg–S Batteries

Mg–S batteries are attractive for next-generation energy storage because of their high theoretical capacity and low cost. The foremost challenge in Mg–S batteries is designing electrolytes that support reversible electrochemistry at both electrodes. Here, we target a solution-mediated reduction pathway for the S_8 cathode by tailoring the electrolyte solvent. Varying the solvent in Mg-based systems is complicated because of the active nature of the solvent in solvating Mg^(2+) and the complex dynamics of electrolyte–Mg interfaces. To understand the effect of the solvent on the S_8 reduction processes in the Mg–S cell, the magnesium–aluminum chloride complex (MACC) electrolyte was prepared in different ethereal solvents. Reversible Mg electrodeposition is demonstrated in the MACC electrolyte in several solvent systems. The electrodeposition overpotentials and current densities are found to vary with the solvent, suggesting that the solvent plays a noninnocent role in the electrochemical processes at the Mg interface. Mg–S cells are prepared with the electrolytes to understand how the solvent affects the reduction of S_8. A reductive wave is present in all linear-sweep voltammograms, and the peak potential varies with the solvent. The peak potential is approximately 0.8 V versus Mg/Mg^(2+), lower than the expected reduction potential of 1.7 V. We rule out passivation of the Mg anode as the cause for the low voltage peak potential, making processes at the S8 cathode the likely culprit. The ability to oxidize MgS with the MACC electrolyte is also examined, and we find that the oxidation current can be attributed to side reactions at the C–electrolyte interface

Effect of the Electrolyte Solvent on Redox Processes in Mg–S Batteries

Mg–S batteries are attractive for next-generation energy storage because of their high theoretical capacity and low cost. The foremost challenge in Mg–S batteries is designing electrolytes that support reversible electrochemistry at both electrodes. Here, we target a solution-mediated reduction pathway for the S_8 cathode by tailoring the electrolyte solvent. Varying the solvent in Mg-based systems is complicated because of the active nature of the solvent in solvating Mg^(2+) and the complex dynamics of electrolyte–Mg interfaces. To understand the effect of the solvent on the S_8 reduction processes in the Mg–S cell, the magnesium–aluminum chloride complex (MACC) electrolyte was prepared in different ethereal solvents. Reversible Mg electrodeposition is demonstrated in the MACC electrolyte in several solvent systems. The electrodeposition overpotentials and current densities are found to vary with the solvent, suggesting that the solvent plays a noninnocent role in the electrochemical processes at the Mg interface. Mg–S cells are prepared with the electrolytes to understand how the solvent affects the reduction of S_8. A reductive wave is present in all linear-sweep voltammograms, and the peak potential varies with the solvent. The peak potential is approximately 0.8 V versus Mg/Mg^(2+), lower than the expected reduction potential of 1.7 V. We rule out passivation of the Mg anode as the cause for the low voltage peak potential, making processes at the S8 cathode the likely culprit. The ability to oxidize MgS with the MACC electrolyte is also examined, and we find that the oxidation current can be attributed to side reactions at the C–electrolyte interface

Experimental demonstration and pan-structurome prediction of climate-associated riboSNitches in Arabidopsis

BACKGROUND: Genome-wide association studies (GWAS) aim to correlate phenotypic changes with genotypic variation. Upon transcription, single nucleotide variants (SNVs) may alter mRNA structure, with potential impacts on transcript stability, macromolecular interactions, and translation. However, plant genomes have not been assessed for the presence of these structure-altering polymorphisms or "riboSNitches." RESULTS: We experimentally demonstrate the presence of riboSNitches in transcripts of two Arabidopsis genes, ZINC RIBBON 3 (ZR3) and COTTON GOLGI-RELATED 3 (CGR3), which are associated with continentality and temperature variation in the natural environment. These riboSNitches are also associated with differences in the abundance of their respective transcripts, implying a role in regulating the gene's expression in adaptation to local climate conditions. We then computationally predict riboSNitches transcriptome-wide in mRNAs of 879 naturally inbred Arabidopsis accessions. We characterize correlations between SNPs/riboSNitches in these accessions and 434 climate descriptors of their local environments, suggesting a role of these variants in local adaptation. We integrate this information in CLIMtools V2.0 and provide a new web resource, T-CLIM, that reveals associations between transcript abundance variation and local environmental variation. CONCLUSION: We functionally validate two plant riboSNitches and, for the first time, demonstrate riboSNitch conditionality dependent on temperature, coining the term "conditional riboSNitch." We provide the first pan-genome-wide prediction of riboSNitches in plants. We expand our previous CLIMtools web resource with riboSNitch information and with 1868 additional Arabidopsis genomes and 269 additional climate conditions, which will greatly facilitate in silico studies of natural genetic variation, its phenotypic consequences, and its role in local adaptation

Does shear wave ultrasound independently predict axillary lymph node metastasis in women with invasive breast cancer?

Shear wave elastography (SWE) shows promise as an adjunct to greyscale ultrasound examination in assessing breast masses. In breast cancer, higher lesion stiffness on SWE has been shown to be associated with features of poor prognosis. The purpose of this study was to assess whether lesion stiffness at SWE is an independent predictor of lymph node involvement. Patients with invasive breast cancer treated by primary surgery, who had undergone SWE examination were eligible. Data were retrospectively analysed from 396 consecutive patients. The mean stiffness values were obtained using the Aixplorer(®) ultrasound machine from SuperSonic Imagine Ltd. Measurements were taken from a region of interest positioned over the stiffest part of the abnormality. The average of the mean stiffness value obtained from each of two orthogonal image planes was used for analysis. Associations between lymph node involvement and mean lesion stiffness, invasive cancer size, histologic grade, tumour type, ER expression, HER-2 status and vascular invasion were assessed using univariate and multivariate logistic regression. At univariate analysis, invasive size, histologic grade, HER-2 status, vascular invasion, tumour type and mean stiffness were significantly associated with nodal involvement. Nodal involvement rates ranged from 7 % for tumours with mean stiffness <50 kPa to 41 % for tumours with a mean stiffness of >150 kPa. At multivariate analysis, invasive size, tumour type, vascular invasion, and mean stiffness maintained independent significance. Mean stiffness at SWE is an independent predictor of lymph node metastasis and thus can confer prognostic information additional to that provided by conventional preoperative tumour assessment and staging

Solid-State Divalent Ion Conduction in ZnPS_3

Next-generation batteries based on divalent working ions have the potential to both reduce the cost of energy storage devices and increase performance. Examples of promising divalent systems include those based on Mg^(2+), Ca^(2+), and Zn^(2+) working ions. Development of such technologies is slow, however, in part due to the difficulty associated with divalent cation conduction in the solid state. Divalent ion conduction is especially challenging in insulating materials that would be useful as solid-state electrolytes or protecting layers on the surfaces of metal anodes. Furthermore, there are no reports of divalent cation conduction in insulating, inorganic materials at reasonable temperatures, prohibiting the development of structure–property relationships. Here, we report Zn^(2+) conduction in insulating ZnPS_3, demonstrating divalent ionic conductivity in an ordered, inorganic lattice near room temperature. Importantly, the activation energy associated with the bulk conductivity is low, 351 ± 99 meV, comparable to some Li+conductors such as LTTO, although not as low as the superionic Li+ conductors. First-principles calculations suggest that the barrier corresponds to vacancy-mediated diffusion. Assessment of the structural distortions observed along the ion diffusion pathways suggests that an increase in the P–P–S bond angle in the [P_2S_6]^(4–) moiety accommodates the Zn^(2+) as it passes through the high-energy intermediate coordination environments. ZnPS_3 now represents a baseline material family to begin developing the structure–property relationships that control divalent ion diffusion and conduction in insulating solid-state hosts

Solid-State Divalent Ion Conduction in ZnPS_3

Next-generation batteries based on divalent working ions have the potential to both reduce the cost of energy storage devices and increase performance. Examples of promising divalent systems include those based on Mg^(2+), Ca^(2+), and Zn^(2+) working ions. Development of such technologies is slow, however, in part due to the difficulty associated with divalent cation conduction in the solid state. Divalent ion conduction is especially challenging in insulating materials that would be useful as solid-state electrolytes or protecting layers on the surfaces of metal anodes. Furthermore, there are no reports of divalent cation conduction in insulating, inorganic materials at reasonable temperatures, prohibiting the development of structure–property relationships. Here, we report Zn^(2+) conduction in insulating ZnPS_3, demonstrating divalent ionic conductivity in an ordered, inorganic lattice near room temperature. Importantly, the activation energy associated with the bulk conductivity is low, 351 ± 99 meV, comparable to some Li+conductors such as LTTO, although not as low as the superionic Li+ conductors. First-principles calculations suggest that the barrier corresponds to vacancy-mediated diffusion. Assessment of the structural distortions observed along the ion diffusion pathways suggests that an increase in the P–P–S bond angle in the [P_2S_6]^(4–) moiety accommodates the Zn^(2+) as it passes through the high-energy intermediate coordination environments. ZnPS_3 now represents a baseline material family to begin developing the structure–property relationships that control divalent ion diffusion and conduction in insulating solid-state hosts

RNA G-Quadruplexes in the model plant species Arabidopsis thaliana: prevalence and possible functional roles

Tandem stretches of guanines can associate in hydrogen-bonded arrays to form G-quadruplexes, which are stabilized by K+ ions. Using computational methods, we searched for G-Quadruplex Sequence (GQS) patterns in the model plant species Arabidopsis thaliana. We found ∼1200 GQS with a G3 repeat sequence motif, most of which are located in the intergenic region. Using a Markov modeled genome, we determined that GQS are significantly underrepresented in the genome. Additionally, we found ∼43 000 GQS with a G2 repeat sequence motif; notably, 80% of these were located in genic regions, suggesting that these sequences may fold at the RNA level. Gene Ontology functional analysis revealed that GQS are overrepresented in genes encoding proteins of certain functional categories, including enzyme activity. Conversely, GQS are underrepresented in other categories of genes, notably those for non-coding RNAs such as tRNAs and rRNAs. We also find that genes that are differentially regulated by drought are significantly more likely to contain a GQS. CD-detected K+ titrations performed on representative RNAs verified formation of quadruplexes at physiological K+ concentrations. Overall, this study indicates that GQS are present at unique locations in Arabidopsis and that folding of RNA GQS may play important roles in regulating gene expression

Age at first birth in women is genetically associated with increased risk of schizophrenia

Prof. Paunio on PGC:n jäsenPrevious studies have shown an increased risk for mental health problems in children born to both younger and older parents compared to children of average-aged parents. We previously used a novel design to reveal a latent mechanism of genetic association between schizophrenia and age at first birth in women (AFB). Here, we use independent data from the UK Biobank (N = 38,892) to replicate the finding of an association between predicted genetic risk of schizophrenia and AFB in women, and to estimate the genetic correlation between schizophrenia and AFB in women stratified into younger and older groups. We find evidence for an association between predicted genetic risk of schizophrenia and AFB in women (P-value = 1.12E-05), and we show genetic heterogeneity between younger and older AFB groups (P-value = 3.45E-03). The genetic correlation between schizophrenia and AFB in the younger AFB group is -0.16 (SE = 0.04) while that between schizophrenia and AFB in the older AFB group is 0.14 (SE = 0.08). Our results suggest that early, and perhaps also late, age at first birth in women is associated with increased genetic risk for schizophrenia in the UK Biobank sample. These findings contribute new insights into factors contributing to the complex bio-social risk architecture underpinning the association between parental age and offspring mental health.Peer reviewe

Antiinflammatory Therapy with Canakinumab for Atherosclerotic Disease

Background: Experimental and clinical data suggest that reducing inflammation without affecting lipid levels may reduce the risk of cardiovascular disease. Yet, the inflammatory hypothesis of atherothrombosis has remained unproved. Methods: We conducted a randomized, double-blind trial of canakinumab, a therapeutic monoclonal antibody targeting interleukin-1β, involving 10,061 patients with previous myocardial infarction and a high-sensitivity C-reactive protein level of 2 mg or more per liter. The trial compared three doses of canakinumab (50 mg, 150 mg, and 300 mg, administered subcutaneously every 3 months) with placebo. The primary efficacy end point was nonfatal myocardial infarction, nonfatal stroke, or cardiovascular death. RESULTS: At 48 months, the median reduction from baseline in the high-sensitivity C-reactive protein level was 26 percentage points greater in the group that received the 50-mg dose of canakinumab, 37 percentage points greater in the 150-mg group, and 41 percentage points greater in the 300-mg group than in the placebo group. Canakinumab did not reduce lipid levels from baseline. At a median follow-up of 3.7 years, the incidence rate for the primary end point was 4.50 events per 100 person-years in the placebo group, 4.11 events per 100 person-years in the 50-mg group, 3.86 events per 100 person-years in the 150-mg group, and 3.90 events per 100 person-years in the 300-mg group. The hazard ratios as compared with placebo were as follows: in the 50-mg group, 0.93 (95% confidence interval [CI], 0.80 to 1.07; P = 0.30); in the 150-mg group, 0.85 (95% CI, 0.74 to 0.98; P = 0.021); and in the 300-mg group, 0.86 (95% CI, 0.75 to 0.99; P = 0.031). The 150-mg dose, but not the other doses, met the prespecified multiplicity-adjusted threshold for statistical significance for the primary end point and the secondary end point that additionally included hospitalization for unstable angina that led to urgent revascularization (hazard ratio vs. placebo, 0.83; 95% CI, 0.73 to 0.95; P = 0.005). Canakinumab was associated with a higher incidence of fatal infection than was placebo. There was no significant difference in all-cause mortality (hazard ratio for all canakinumab doses vs. placebo, 0.94; 95% CI, 0.83 to 1.06; P = 0.31). Conclusions: Antiinflammatory therapy targeting the interleukin-1β innate immunity pathway with canakinumab at a dose of 150 mg every 3 months led to a significantly lower rate of recurrent cardiovascular events than placebo, independent of lipid-level lowering. (Funded by Novartis; CANTOS ClinicalTrials.gov number, NCT01327846.