Ab Initio Molecular Dynamics Study of Aqueous Solvation of Ethanol and Ethylene

The structure and dynamics of aqueous solvation of ethanol and ethylene are studied by DFT-based Car-Parrinello molecular dynamics. We did not find an enhancement of the structure of the hydrogen bonded network of hydrating water molecules. Both ethanol and ethylene can easily be accommodated in the hydrogen-bonded network of water molecules without altering its structure. This is supports the conclusion from recent neutron diffraction experiments that there is no hydrophobic hydration around small hydrophobic groups. Analysis of the electronic charge distribution using Wannier functions shows that the dipole moment of ethanol increases from 1.8 D to 3.1 D upon solvation, while the apolar ethylene molecule attains an average dipole moment of 0.5 D. For ethylene, we identified configurations with $\pi$-H bonded water molecules, that have rare four-fold hydrogen-bonded water coordination, yielding instantaneous dipole moments of ethylene of up to 1 D. The results provide valuable information for the improvement of empirical force fields, and point out that for an accurate description of the aqueous solvation of ethanol, and even of the apolar ethylene, polarizable force fields are required.Comment: 15 pages, 10 figures, 4 tables, revtex4, submitted to J. Chem. Phy

Radicals in carbonaceous residue deposited on mordenite from methanol

It is shown that control of the degree of coking can lead to the observation of hyperfine structures in the carbonaceous residues deposited from methanol over mordenite (H-MOR) at temperatures relevant to the conversion of methanol to hydrocarbons. EPR measurements of the catalyst samples at various times on stream have been recorded, with a rich hyperfine splitting pattern observed in the early stages of the reaction. Interpretation of the EPR data with the aid of density functional theoretical calculations has afforded the first definitive assignment of the radical cations formed in high temperature coke. The results detail a shortlist of six species: 2,3/2,6/2,7-dimethylnaphthalenium, 2,3,6-trimethylnaphthalenium, 2,3,6,7-tetramethylnaphthalenium, and anthracenium radical cations whose proton hyperfine splitting profiles match the experimental spectra; 2,3,6,7-tetramethylnaphthalenium showed the best agreement. The observation of these particular isomers of polymethylnaphthalene suggest the formation of more highly branched polyaromatic species is less likely within the confines of the H-MOR 12-membered ring channel. These radicals formed when the catalyst is active may constitute key intermediates in the conversion of methanol to light olefins

Out-of-plane magnetic domain structure in a thin film of La0.67Sr0.33MnO3 on SrTiO3 (001) observed by magnetic force microscopy

The room temperature out-of-plane magnetization of epitaxial thin films of La0.67Sr0.33MnO3 on SrTiO3 (001) has been investigated with magnetic force microscopy, using magnetic tips with very small coercivity, relative to the film. A clear magnetic pattern in the form of a checkerboard, with domain dimensions of a few hundred nanometers, was found for the thin, coherently strained films, which is approximately aligned along the maximum strain [110] and [1[overline 1]0] directions in the film. With increasing in-plane applied magnetic field, the magnetic contrast reduces, reflecting the rotation of the magnetization vector into the plane of the film. This process is reversible with the field. The out-of-plane magnetic pattern is not sensitive to rotation of the in-plane field. We attribute the observed out-of-plane magnetization component to an out-of-plane magnetic anisotropy, which is a remainder of the [111] magnetic easy axis in bulk La0.67Sr0.33MnO3 single crystal

Dynamic balance and ankle injury odds: a prospective study in 196 Dutch physical education teacher education students

OBJECTIVE: The aim of this study was to investigate whether dynamic balance, measured with the anterior component of the Star Excursion Balance Test (SEBT-ANT), is a risk factor for ankle injuries in physical education tea

Predicting semantic labels of text regions in heterogeneous document images

Contains fulltext : 214639.pdf (publisher's version ) (Open Access)KONVENS 2019: 15th Conference on Natural Language Processing, Erlangen, Germany, October 9-11, 201

Is your system fit for purpose? Female athlete health considerations for rugby injury and illness surveillance systems

This review discusses female-specific health considerations in injury and illness surveillance and provides rugby-specific recommendations for future surveillance. Identifying priority injury and illness problems by determining those problems with the highest rates within women's rugby may highlight different priorities than sex comparisons between men's and women's rugby. Whilst sports exposure is the primary risk for health problems in sports injury and illness surveillance, female athletes have health domains that should also be considered. Alongside female athlete health domains, studies investigating rugby injuries and illnesses highlight the need to broaden the health problem definition typically used in rugby injury and illness surveillance. Using a non-time-loss health problem definition, recording female-specific population characteristics, embedding female athlete health domains and having up-to-date injury and illness coding systems should be prioritized within surveillance systems to begin to shed light on potential interactions between sports exposure, health domains and, injuries and illnesses. We call for a collaborative approach across women's rugby to facilitate large injury and illness datasets to be generated and enable granular level categorization and analysis, which may be necessary for certain female athlete health domains. Applying these recommendations will ensure injury and illness surveillance systems improve risk identification and better inform injury and illness prevention strategies in women's rugby

Frontal plane roll-over analysis of prosthetic feet

In prosthetic walking mediolateral balance is compromised due to the lack of active ankle control, by moments of force, in the prosthetic limb. Active control is reduced to the hip strategy, and passive mechanical stability depends on the curvature of the prosthetic foot under load. Mediolateral roll-over curvatures of prosthetic feet are largely unknown. In this study we determined the mediolateral roll-over characteristics of various prosthetic feet and foot-shoe combinations. Characteristics were determined by means of an inverted pendulum-like apparatus. The relationship between the centre of pressure (CoP) and the shank angle was measured and converted to roll-over shape and effective radius of curvature. Further, hysteresis (i.e., lagging in CoP displacement due to material compliance or slip) at vertical shank angle was determined from the hysteresis curve. Passive mechanical stability varied widely, though all measured foot-shoe combinations were relatively compliant. Mediolateral motion of the CoP ranged between 4 mm and 40 mm, thereby remaining well within each foot's physical width. Derived roll-over radii of curvature are also small, with an average of 102 mm. Hysteresis ranges between 20% and 115% of total CoP displacement and becomes more pronounced when adding a shoe. This may be due to slipping of the foot core in its cosmetic cover, or the foot in the shoe. Slip may be disadvantageous for balance control by limiting mediolateral travel of the CoP. It may therefore be clinically relevant to eliminate mediolateral slip in prosthetic foot design

Hydration of methanol in water. A DFT-based molecular dynamics study

We studied the hydration of a single methanol molecule in aqueous solution by first-principle DFT-based molecular dynamics simulation. The calculations show that the local structural and short-time dynamical properties of the water molecules remain almost unchanged by the presence of the methanol, confirming the observation from recent experimental structural data for dilute solutions. We also see, in accordance with this experimental work, a distinct shell of water molecules that consists of about 15 molecules. We found no evidence for a strong tangential ordering of the water molecules in the first hydration shell.Comment: 5 pages, 3 figures, submitted to Chemical Physics Letter