Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.K.O acknowledges a research fellowship from Japanese Society for the Promotion of Science (JSPS). E.S acknowledges support by a Marie Curie Intra European Fellowship within the 7th European Community Framework Programme and thanks Churchill College (Cambridge, UK) for a non-stipendiary Raymond and Beverly Sackler Research fellowship. C.J.K and A.E.F acknowledge a research studentship from the Cambridge Nano Science and Technology Doctoral Training Centre (NanoDTC). A.J.M acknowledges the support from the Winton Programme for the Physics of Sustainability. S.H acknowledges funding from ERC grant InsituNANO (project number 279342). C.P.G and C.D thank the Royal Society, and C.P.G thanks European Research Council (ERC). C.P.G. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy, under Contract DE-AC02-05CH11231, subcontract 6952000.This is the accepted manuscript. The final version is available from Nature Communications at http://www.nature.com/ncomms/2014/140203/ncomms4217/full/ncomms4217.html

Large perturbations in CO2 flux and subsequent chemosynthesis are induced in agricultural soil by the addition of elemental sulfur

The microbial contribution to soil organic matter has been shown to be much larger than previously thought and thus it plays a major role in carbon cycling. Among soil microorganisms, chemoautotrophs can fix CO2 without sunlight and can glean energy through the oxidation of reduced elements such as sulfur. Here we show that the addition of sulfur to soil results in an initial surge in production of CO2 through microbial respiration, followed by an order of magnitude increase in the capture of carbon from the atmosphere as elemental sulfur is oxidised to sulfate. Thiobacillus spp., take advantage of specific conditions to become the dominant chemoautotrophic group that consumes CO2. We discern the direct incorporation of atmospheric carbon into soil carbohydrate, protein and aliphatic compounds and differentiate these from existing biomass. These results suggest that chemoautotrophs can play a large role in carbon cycling and that this carbon is heavily influenced by land management practises

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centers. We demonstrate how the single-ion electron paramagnetic resonance $\textbf{g}$ tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the $\textbf{g}$ tensor with density functional theory to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, $\textbf{σ}$$^{s}$. The method is applied to a series of olivine-type Li$\textit{TM}$PO$_{4}$ materials (with $\textit{TM}$=Mn, Fe, Co, and Ni) and the corresponding $^{7}$$\textbf{Li}$ and $^{31}$$\textbf{P}$ NMR spectra are simulated. We analyze the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the Li$\textit{TM}$PO$_{4}$ series, in which the magnitudes and signs of the nonrelativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.RP acknowledges financial support from the People Programme (Marie Curie Ac- tions) of the European Union’s Seventh Framework Pro- gramme (FP7/2007-2013) under REA grant agreement n◦ 317127. Via our membership of the U.K.’s HPC Materials Chemistry Consortium, which is funded by EPSRC (n ◦ EP/L000202), this work made use of the facilities of ARCHER, the U.K.’s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC’s High End Computing Programme. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Lab- oratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract n◦ DE-AC02-98CH10886

Investigating Sodium Storage Mechanisms in Tin Anodes: A Combined Pair Distribution Function Analysis, Density Functional Theory and Solid-State NMR Approach

The alloying mechanism of high-capacity tin anodes for sodium-ion batteries is investigated using a combined theoretical and experimental approach. Ab initio random structure searching (AIRSS) and high-throughput screening using a species-swap method provide insights into a range of possible sodium-tin structures. These structures are linked to experiments using both average and local structure probes in the form of operando pair distribution function analysis, X-ray diffraction, and 23Na solid-state nuclear magnetic resonance (ssNMR), and ex situ 119Sn ssNMR. Through this approach, we propose structures for the previously unidentified crystalline and amorphous intermediates. The first electrochemical process of sodium insertion into tin results in the conversion of crystalline tin into a layered structure consisting of mixed Na/Sn occupancy sites intercalated between planar hexagonal layers of Sn atoms (approximate stoichiometry NaSn3). Following this, NaSn2, which is predicted to be thermodynamically stable by AIRSS, forms; this contains hexagonal layers closely related to NaSn3, but has no tin atoms between the layers. NaSn2 is broken down into an amorphous phase of approximate composition Na1.2Sn. Reverse Monte Carlo refinements of an ab initio molecular dynamics model of this phase show that the predominant tin connectivity is chains. Further reaction with sodium results in the formation of structures containing Sn-Sn dumbbells, which interconvert through a solid-solution mechanism. These structures are based upon Na5-xSn2, with increasing occupancy of one of its sodium sites commensurate with the amount of sodium added. ssNMR results indicate that the final product, Na15Sn4, can store additional sodium atoms as an off-stoichiometry compound (Na15+xSn4) in a manner similar to Li15Si4.This work was supported by STFCBatteries.org through the STFC Futures Early Career Award (J.M.S.). J.M.S. acknowledges funding from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, of the U.S. DOE under Contract no. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract no. 7057154, and the European Commission under grant agreement no. 696656 (Graphene Flagship). P.K.A. acknowledges the School of the Physical Sciences of the University of Cambridge for funding through an Oppenheimer Research Fellowship and a Junior Research Fellowship from Gonville and Caius College, Cambridge. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 655444 (O.P.). M.M. and A.J.M. acknowledge the support from the Winton Programme for the Physics of Sustainability. A.J.M. and C.J.P. were supported by Engineering and Physical Sciences Research Council (EPSRC) of the United Kingdom (Grant no. EP/G007489/2). C.J.P. is also supported by the Royal Society through a Royal Society Wolfson Research Merit award. Calculations were performed using the Archer facility of the UK national high performance computing service, for which access was obtained via the UKCP consortium and funded by EPSRC grant no. EP/K014560/1

Genetic Crossovers Are Predicted Accurately by the Computed Human Recombination Map

Hotspots of meiotic recombination can change rapidly over time. This instability and the reported high level of inter-individual variation in meiotic recombination puts in question the accuracy of the calculated hotspot map, which is based on the summation of past genetic crossovers. To estimate the accuracy of the computed recombination rate map, we have mapped genetic crossovers to a median resolution of 70 Kb in 10 CEPH pedigrees. We then compared the positions of crossovers with the hotspots computed from HapMap data and performed extensive computer simulations to compare the observed distributions of crossovers with the distributions expected from the calculated recombination rate maps. Here we show that a population-averaged hotspot map computed from linkage disequilibrium data predicts well present-day genetic crossovers. We find that computed hotspot maps accurately estimate both the strength and the position of meiotic hotspots. An in-depth examination of not-predicted crossovers shows that they are preferentially located in regions where hotspots are found in other populations. In summary, we find that by combining several computed population-specific maps we can capture the variation in individual hotspots to generate a hotspot map that can predict almost all present-day genetic crossovers

Terrestrial support of lake food webs: Synthesis reveals controls over cross-ecosystem resource use

Widespread evidence that organic matter exported from terrestrial into aquatic ecosystems supports recipient food webs remains controversial. A pressing question is not only whether high terrestrial support is possible but also what the general conditions are under which it arises. We assemble the largest data set, to date, of the isotopic composition (δ$^{2}$H, δ$^{13}$C, and δ$^{15}$N) of lake zooplankton and the resources at the base of their associated food webs. In total, our data set spans 559 observations across 147 lakes from the boreal to subtropics. By predicting terrestrial resource support from within-lake and catchment-level characteristics, we found that half of all consumer observations that is, the median were composed of at least 42% terrestrially derived material. In general, terrestrial support of zooplankton was greatest in lakes with large physical and hydrological connections to catchments that were rich in aboveground and belowground organic matter. However, some consumers responded less strongly to terrestrial resources where within-lake production was elevated. Our study shows that multiple mechanisms drive widespread cross-ecosystem support of aquatic consumers across Northern Hemisphere lakes and suggests that changes in terrestrial landscapes will influence ecosystem processes well beyond their boundaries.Support to organize the working group that produced this manuscript came from Natural Environment Research Council grant NE/M005968/1. B.W.K. also received travel support from the Natural Sciences and Engineering Research Council of Canada Collaborative Research and Training Experiencein Biodiversity Research at the University of British Columbia. J.K. received funding from the Swedish Research Council (2012–2015, funding number 621-2011-3908). M.L.P. acknowledges funding from the NSF Division of Environmental Biology (grant number 1456151)

Anterior anal sphincter repair can be of long term benefit: a 12-year case cohort from a single surgeon

BACKGROUND: Early surgical results of anterior sphincter repair for faecal incontinence can be good, but in the longer term are often disappointing. This study aimed to determine the short and long term outcomes from anterior sphincter repair and identify factors predictive of long term success. METHODS: Patients who underwent anterior sphincter repair between 1989 and 2001 in one institution were identified. Postal questionnaires were sent to patients, which included validated scoring systems for symptom severity and quality of life assessments for faecal incontinence. Patient demographics and risk factors were recorded as were the results of anorectal physiology studies and endoanal ultrasound. RESULTS: Eighty-five patients underwent repair by one consultant. The length of follow up ranged from 1 to 12 years. Most patients (96%) had early symptom improvement postoperatively. Of the 47 patients assessed long term (≥ 5 years), 28 (60%) maintained this success. Significant improvements in quality of life were observed (P < 0.001). Neither patient, surgical nor anorectal physiology study parameters were predictive of outcome. CONCLUSION: There were no predictive factors of outcome success and no changes in anal manometry identified, however anterior sphincter repair remains worthwhile. Changes in compliance of the anorectum may be responsible for symptom improvement

Local Structure Evolution and Modes of Charge Storage in Secondary Li-FeS2_{2} Cells

In the pursuit of high-capacity electrochemical energy storage, a promising domain of research involves conversion reaction schemes, wherein electrode materials are fully transformed during charge and discharge. There are, however, numerous difficulties in realizing theoretical capacity and high rate capability in many conversion schemes. Here we employ operando studies to understand the conversion material FeS$_{2}$, focusing on the local structure evolution of this relatively reversible material. X-ray absorption spectroscopy, pair distribution function analysis, and first-principles calculations of intermediate structures shed light on the mechanism of charge storage in the Li-FeS$_{2}$ system, with some general principles emerging for charge storage in chalcogenide materials. Focusing on second and later charge/discharge cycles, we find small, disordered domains that locally resemble Fe and Li$_{2}$S at the end of the first discharge. Upon charge, this is converted to a Li-Fe-S composition whose local structure reveals tetrahedrally coordinated Fe. With continued charge, this ternary composition displays insertion-extraction behavior at higher potentials and lower Li content. The finding of hybrid modes of charge storage, rather than simple conversion, points to the important role of intermediates that appear to store charge by mechanisms that more closely resemble intercalation.M.M.B. acknowledges support by the Fletcher Jones and Peter J. Frenkel Foundation Fellowships. V.V.T.D.-N. is supported by the University of California President’s Postdoctoral Fellowship and the UCSB California NanoSystems Institute Elings Prize Fellowship. V.V.T.D.-N. gratefully acknowledges the Southern California Electrochemical Energy Storage Alliance (SCEESA), supported by the UCSB CNSI. Experiments at UCSB made use of MRL facilities, supported by the MRSEC Program of the NSF under Grant No. NSF-DMR 1121053. M.A.L. was supported by the RISE program through Grant No. NSF-DMR 1121053. This work was partially supported by the IMI Program of the National Science Foundation under Award No. DMR 08-43934. M.M. and A.J.M. acknowledge the support from the Winton Programme for the Physics of Sustainability. C.P.G. and S.B. thank EPSRC for financial support. This research made use of resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. X-ray absorption experiments were performed at APS 20-BM-B under GUP-41555. Sector 20 operations are supported by the U.S. DOE and the Canadian Light Source. X-ray scattering experiments were performed at APS 11-ID-B under GUP-42128 and GUP-45245

Molecular analysis of the vaginal response to estrogens in the ovariectomized rat and postmenopausal woman

<p>Abstract</p> <p>Background</p> <p>Vaginal atrophy (VA) is the thinning of the vaginal epithelial lining, typically the result of lowered estrogen levels during menopause. Some of the consequences of VA include increased susceptibility to bacterial infection, pain during sexual intercourse, and vaginal burning or itching. Although estrogen treatment is highly effective, alternative therapies are also desired for women who are not candidates for post-menopausal hormone therapy (HT). The ovariectomized (OVX) rat is widely accepted as an appropriate animal model for many estrogen-dependent responses in humans; however, since reproductive biology can vary significantly between mammalian systems, this study examined how well the OVX rat recapitulates human biology.</p> <p>Methods</p> <p>We analyzed 19 vaginal biopsies from human subjects pre and post 3-month 17β-estradiol treated by expression profiling. Data were compared to transcriptional profiling generated from vaginal samples obtained from ovariectomized rats treated with 17β-estradiol for 6 hrs, 3 days or 5 days. The level of differential expression between pre- vs. post- estrogen treatment was calculated for each of the human and OVX rat datasets. Probe sets corresponding to orthologous rat and human genes were mapped to each other using NCBI Homologene.</p> <p>Results</p> <p>A positive correlation was observed between the rat and human responses to estrogen. Genes belonging to several biological pathways and GO categories were similarly differentially expressed in rat and human. A large number of the coordinately regulated biological processes are already known to be involved in human VA, such as inflammation, epithelial development, and EGF pathway activation.</p> <p>Conclusion</p> <p>At the transcriptional level, there is evidence of significant overlap of the effects of estrogen treatment between the OVX rat and human VA samples.</p

Prdm9, a Major Determinant of Meiotic Recombination Hotspots, Is Not Functional in Dogs and Their Wild Relatives, Wolves and Coyotes

Meiotic recombination is a fundamental process needed for the correct segregation of chromosomes during meiosis in sexually reproducing organisms. In humans, 80% of crossovers are estimated to occur at specific areas of the genome called recombination hotspots. Recently, a protein called PRDM9 was identified as a major player in determining the location of genome-wide meiotic recombination hotspots in humans and mice. The origin of this protein seems to be ancient in evolutionary time, as reflected by its fairly conserved structure in lineages that diverged over 700 million years ago. Despite its important role, there are many animal groups in which Prdm9 is absent (e.g. birds, reptiles, amphibians, diptera) and it has been suggested to have disruptive mutations and thus to be a pseudogene in dogs. Because of the dog's history through domestication and artificial selection, we wanted to confirm the presence of a disrupted Prdm9 gene in dogs and determine whether this was exclusive of this species or whether it also occurred in its wild ancestor, the wolf, and in a close relative, the coyote. We sequenced the region in the dog genome that aligned to the last exon of the human Prdm9, containing the entire zinc finger domain, in 4 dogs, 17 wolves and 2 coyotes. Our results show that the three canid species possess mutations that likely make this gene non functional. Because these mutations are shared across the three species, they must have appeared prior to the split of the wolf and the coyote, millions of years ago, and are not related to domestication. In addition, our results suggest that in these three canid species recombination does not occur at hotspots or hotspot location is controlled through a mechanism yet to be determined