Orientational correlations in liquid acetone and dimethyl sulfoxide: A comparative study

The structure of acetone and dimethyl sulfoxide in the liquid state is investigated using a combination of neutron diffractionmeasurements and empirical potential structure refinement (EPSR) modeling. By extracting the orientational correlations from the EPSR model, the alignment of dipoles in both fluids is identified. At short distances the dipoles or neighboring molecules are found to be in antiparallel configurations, but further out the molecules tend to be aligned predominately as head to tail in the manner of dipolar ordering. The distribution of these orientations in space around a central molecule is strongly influenced by the underlying symmetry of the central molecule. In both liquids there is evidence for weak methyl hydrogen to oxygen intermolecular contacts, though these probably do not constitute hydrogen bonds as such

Investigations on the structure of dimethyl sulfoxide and acetone in aqueous solution

Aqueous solutions of dimethyl sulfoxide (DMSO) and acetone have been investigated using neutron diffraction augmented with isotopic substitution and empirical potential structure refinement computer simulations. Each solute has been measured at two concentrations—1:20 and 1:2 solute:water mole ratios. At both concentrations for each solute, the tetrahedral hydrogen bonding network of water is largely unperturbed, though the total water molecule coordination number is reduced in the higher 1:2 concentrations. With higher concentrations of acetone, water tends to segregate into clusters, while in higher concentrations of DMSO the present study reconfirms that the structure of the liquid is dominated by DMSO-water interactions. This result may have implications for the highly nonideal behavior observed in the thermodynamic functions for 1:2 DMSO-water solutions

A Neutron Diffraction Study of the Electrochemical Double Layer Capacitor Electrolyte Tetrapropylammonium Bromide in Acetonitrile.

Neutron diffraction with isotopic substitution has been used to characterize the bulk liquid structure of the technologically relevant electrolyte solution, 1 M tetrapropylammonium bromide (TPA Br) in acetonitrile (acn), and of pure deuterated acetonitrile. Empirical potential structure refinement modeling procedures have been used to extract detailed structural information about solvent-solvent, solvent-ion, and ion-ion correlations. Analysis of the refined data shows the expected local dipolar conformation of acn in the pure solvent. This short-range dipolar ordering is also present within the solutions of TPA Br in acn, and it affects how the solvent orders itself around the ions. The solvation numbers of the TPA cations and the bromide anions are deduced, 8 and 5, respectively, as are the orientations of the solvent molecules that surround the ions. Evidence for ion association is also presented, with nearly two-thirds of the ions in the system being in associated pairs or clusters.E.K.H. acknowledges the European Research Council ERC Grant ERC-2009-AdG-247411 for funding. P.K.A acknowledges a Junior Research Fellowship from Gonville and Caius College, an Oppenheimer Fellowship from the University of Cambridge. R.J.L.W. acknowledges the EPSRC Grant 11220426 for funding.This is the author accepted manuscript. The final version is available from ACS via http://dx.doi.org/10.1021/acs.jpcb.5b0824

Remotely Sensed Canopy Nitrogen Correlates With Nitrous Oxide Emissions in a Lowland Tropical Rainforest

Tropical forests exhibit significant heterogeneity in plant functional and chemical traits that may contribute to spatial patterns of key soil biogeochemical processes, such as carbon storage and greenhouse gas emissions. Although tropical forests are the largest ecosystem source of nitrous oxide (N2O), drivers of spatial patterns within forests are poorly resolved. Here, we show that local variation in canopy foliar N, mapped by remote‐sensing image spectroscopy, correlates with patterns of soil N2O emission from a lowland tropical rainforest. We identified ten 0.25 ha plots (assemblages of 40–70 individual trees) in which average remotely‐sensed canopy N fell above or below the regional mean. The plots were located on a single minimally‐dissected terrace (km2) where soil type, vegetation structure and climatic conditions were relatively constant. We measured N2O fluxes monthly for 1 yr and found that high canopy N species assemblages had on average three‐fold higher total mean N2O fluxes than nearby lower canopy N areas. These differences are consistent with strong differences in litter stoichiometry, nitrification rates and soil nitrate concentrations. Canopy N status was also associated with microbial community characteristics: lower canopy N plots had two‐fold greater soil fungal to bacterial ratios and a significantly lower abundance of ammonia‐oxidizing archaea, although genes associated with denitrification (nirS, nirK, nosZ) showed no relationship with N2O flux. Overall, landscape emissions from this ecosystem are at the lowest end of the spectrum reported for tropical forests, consist with multiple metrics indicating that these highly productive forests retain N tightly and have low plant‐available losses. These data point to connections between canopy and soil processes that have largely been overlooked as a driver of denitrification. Defining relationships between remotely‐sensed plant traits and soil processes offers the chance to map these processes at large scales, potentially increasing our ability to predict N2O emissions in heterogeneous landscapes

Refined conditions for V-shaped optimal sequencing on a single machine to minimize total completion time under combined effects

We address single machine scheduling problems for which the actual processing times of jobs are subject to various effects, including a positional effect, a cumulative effect and their combination. We review the known results on the problems to minimize the makespan, the sum of the completion times and their combinations and identify the problems for which an optimal sequence cannot be found by simple priority rules such as SPT (Shortest Processing Time) and/or LPT (Longest Processing Time). Typically, these are problems to minimize the sum of the completion times under a deterioration effect, and we verify under which conditions for these problems an optimal permutation is V-shaped (an LPT subsequence followed by an SPT subsequence). We demonstrate that previously used techniques for proving that an optimal sequence is V- shaped are not properly justified. We use the corrected method to describe a wide range of problems with a pure positional effect and a combination of a cumulative effect with a positional effect for which an optimal sequence is V-shaped. On other hand, we show that even the refined approach has its limitations

Analysis of shared heritability in common disorders of the brain

ience, this issue p. eaap8757 Structured Abstract INTRODUCTION Brain disorders may exhibit shared symptoms and substantial epidemiological comorbidity, inciting debate about their etiologic overlap. However, detailed study of phenotypes with different ages of onset, severity, and presentation poses a considerable challenge. Recently developed heritability methods allow us to accurately measure correlation of genome-wide common variant risk between two phenotypes from pools of different individuals and assess how connected they, or at least their genetic risks, are on the genomic level. We used genome-wide association data for 265,218 patients and 784,643 control participants, as well as 17 phenotypes from a total of 1,191,588 individuals, to quantify the degree of overlap for genetic risk factors of 25 common brain disorders. RATIONALE Over the past century, the classification of brain disorders has evolved to reflect the medical and scientific communities' assessments of the presumed root causes of clinical phenomena such as behavioral change, loss of motor function, or alterations of consciousness. Directly observable phenomena (such as the presence of emboli, protein tangles, or unusual electrical activity patterns) generally define and separate neurological disorders from psychiatric disorders. Understanding the genetic underpinnings and categorical distinctions for brain disorders and related phenotypes may inform the search for their biological mechanisms. RESULTS Common variant risk for psychiatric disorders was shown to correlate significantly, especially among attention deficit hyperactivity disorder (ADHD), bipolar disorder, major depressive disorder (MDD), and schizophrenia. By contrast, neurological disorders appear more distinct from one another and from the psychiatric disorders, except for migraine, which was significantly correlated to ADHD, MDD, and Tourette syndrome. We demonstrate that, in the general population, the personality trait neuroticism is significantly correlated with almost every psychiatric disorder and migraine. We also identify significant genetic sharing between disorders and early life cognitive measures (e.g., years of education and college attainment) in the general population, demonstrating positive correlation with several psychiatric disorders (e.g., anorexia nervosa and bipolar disorder) and negative correlation with several neurological phenotypes (e.g., Alzheimer's disease and ischemic stroke), even though the latter are considered to result from specific processes that occur later in life. Extensive simulations were also performed to inform how statistical power, diagnostic misclassification, and phenotypic heterogeneity influence genetic correlations. CONCLUSION The high degree of genetic correlation among many of the psychiatric disorders adds further evidence that their current clinical boundaries do not reflect distinct underlying pathogenic processes, at least on the genetic level. This suggests a deeply interconnected nature for psychiatric disorders, in contrast to neurological disorders, and underscores the need to refine psychiatric diagnostics. Genetically informed analyses may provide important "scaffolding" to support such restructuring of psychiatric nosology, which likely requires incorporating many levels of information. By contrast, we find limited evidence for widespread common genetic risk sharing among neurological disorders or across neurological and psychiatric disorders. We show that both psychiatric and neurological disorders have robust correlations with cognitive and personality measures. Further study is needed to evaluate whether overlapping genetic contributions to psychiatric pathology may influence treatment choices. Ultimately, such developments may pave the way toward reduced heterogeneity and improved diagnosis and treatment of psychiatric disorders