1,828 research outputs found
Crystal Structures of Polymerized Fullerides AC60, A=K, Rb, Cs and Alkali-mediated Interactions
Starting from a model of rigid interacting C60 polymer chains on an
orthorhombic lattice, we study the mutual orientation of the chains and the
stability of the crystalline structures Pmnn and I2/m. We take into account i)
van der Waals interactions and electric quadrupole interactions between C60
monomers on different chains as well as ii) interactions of the monomers with
the surrounding alkali atoms. The direct interactions i) always lead to an
antiferrorotational structure Pmnn with alternate orientation of the C60 chains
in planes (001). The interactions ii) with the alkalis consist of two parts:
translation-rotation (TR) coupling where the orientations of the chains
interact with displacements of the alkalis, and quadrupolar electronic
polarizability (ep) coupling, where the electric quadrupoles on the C60
monomers interact with induced quadrupoles due to excited electronic d states
of the alkalis. Both interactions ii) lead to an effective
orientation-orientation interaction between the C60 chains and always favor the
ferrorotational structure I2/m where C60 chains have a same orientation. The
structures Pmnn for KC60 and I2/m for Rb- and CsC60 are the result of a
competition between the direct interaction i) and the alkali-mediated
interactions ii). In Rb- and CsC60 the latter are found to be dominant, the
preponderant role being played by the quadrupolar electronic polarizability of
the alkali ions.Comment: J.Chem.Phys., in press, 14 pages, 3 figures, 8 table
State-to-State Differential and Relative Integral Cross Sections for Rotationally Inelastic Scattering of H2O by Hydrogen
State-to-state differential cross sections (DCSs) for rotationally inelastic
scattering of H2O by H2 have been measured at 71.2 meV (574 cm-1) and 44.8 meV
(361 cm-1) collision energy using crossed molecular beams combined with
velocity map imaging. A molecular beam containing variable compositions of the
(J = 0, 1, 2) rotational states of hydrogen collides with a molecular beam of
argon seeded with water vapor that is cooled by supersonic expansion to its
lowest para or ortho rotational levels (JKaKc= 000 and 101, respectively).
Angular speed distributions of fully specified rotationally excited final
states are obtained using velocity map imaging. Relative integral cross
sections are obtained by integrating the DCSs taken with the same experimental
conditions. Experimental state-specific DCSs are compared with predictions from
fully quantum scattering calculations on the most complete H2O-H2 potential
energy surface. Comparison of relative total cross sections and state-specific
DCSs show excellent agreement with theory in almost all detailsComment: 46 page
Extended Huckel theory for bandstructure, chemistry, and transport. II. Silicon
In this second paper, we develop transferable semi-empirical parameters for
the technologically important material, silicon, using Extended Huckel Theory
(EHT) to calculate its electronic structure. The EHT-parameters areoptimized to
experimental target values of the band dispersion of bulk-silicon. We obtain a
very good quantitative match to the bandstructure characteristics such as
bandedges and effective masses, which are competitive with the values obtained
within an orthogonal-tight binding model for silicon. The
transferability of the parameters is investigated applying them to different
physical and chemical environments by calculating the bandstructure of two
reconstructed surfaces with different orientations: Si(100) (2x1) and Si(111)
(2x1). The reproduced - and -surface bands agree in part
quantitatively with DFT-GW calculations and PES/IPES experiments demonstrating
their robustness to environmental changes. We further apply the silicon
parameters to describe the 1D band dispersion of a unrelaxed rectangular
silicon nanowire (SiNW) and demonstrate the EHT-approach of surface passivation
using hydrogen. Our EHT-parameters thus provide a quantitative model of
bulk-silicon and silicon-based materials such as contacts and surfaces, which
are essential ingredients towards a quantitative quantum transport simulation
through silicon-based heterostructures.Comment: 9 pages, 9 figure
A tight binding model for water
We demonstrate for the first time a tight binding model for water
incorporating polarizable anions. A novel aspect is that we adopt a "ground up"
approach in that properties of the monomer and dimer only are fitted.
Subsequently we make predictions of the structure and properties of hexamer
clusters, ice-XI and liquid water. A particular feature, missing in current
tight binding and semiempirical hamiltonians, is that we reproduce the almost
two-fold increase in molecular dipole moment as clusters are built up towards
the limit of bulk liquid. We concentrate on properties of liquid water which
are very well rendered in comparison with experiment and published density
functional calculations. Finally we comment on the question of the contrasting
densities of water and ice which is central to an understanding of the
subtleties of the hydrogen bond
IL-21 receptor expression in human tendinopathy
The pathogenetic mechanisms underlying tendinopathy remain unclear,
with much debate as to whether inflammation or degradation has the prominent
role. Increasing evidence points toward and early inflammatory infiltrate and
associated inflammatory cytokine production in human and animal models of
tendon disease.
The IL-21/IL-21R axis is a proinflammatory cytokine complex that has
been associated with chronic inflammatory diseases including rheumatoid
arthritis and inflammatory bowel disease. This project aimed to investigate the
role and expression of the cytokine/receptor pair IL-21/IL-21R in human
tendinopathy.
We found significantly elevated expression of IL-21 receptor message and
protein in human tendon samples but found no convincing evidence of the
presence of IL-21 at message or protein level. The level of expression of IL-21R
message/protein in human tenocytes was significantly up regulated by
proinflammatory cytokines (TNFα/IL-1β) in vitro.
These findings demonstrate that IL-21R is present in early human
tendinopathy mainly expressed by tenocytes and macrophages. Despite a lack of
IL-21 expression these data again suggest that early tendinopathy has an
inflammatory/cytokine phenotype, which may provide novel translational targets
in the treatment of tendinopathy
A multicentre, prospective, randomised, blinded clinical trial to compare some perioperative effects of buprenorphine or butorphanol premedication before equine elective general anaesthesia and surgery
REASONS FOR PERFORMING STUDY: Buprenorphine, a μ‐agonist opioid, has recently been licensed for equine use, but butorphanol, a κ‐agonist opioid, is more commonly used in horses. The effect of the 2 opioids has not previously been compared in a large clinical study. OBJECTIVES: To compare post operative analgesia and physiological variables in horses undergoing elective surgery following premedication with either buprenorphine or butorphanol in a conventional clinical setting. STUDY DESIGN: Multicentre, prospective, randomised, blinded clinical investigation. METHODS: Eighty‐nine healthy horses admitted for elective surgery to one of 6 UK equine veterinary clinics were premedicated with acepromazine, a nonsteroidal anti‐inflammatory drug, and romifidine followed by intravenous (i.v.) buprenorphine or butorphanol. Anaesthesia was induced with diazepam/ketamine and maintained with isoflurane in oxygen. A range of surgical procedures were performed and supplementary anaesthetic agents given as required. Physiological variables were monitored during anaesthesia and pain, ataxia, sedation and vital function were assessed post operatively. Data were analysed using t‐tests, ANOVA, Mann–Whitney U‐test and Chi‐squared test as appropriate and P<0.05 was regarded as significant, except for multiple comparisons, when P<0.01 was used. RESULTS: Surgery was carried out successfully in all cases and no mortality or serious morbidity occurred. Physiological variables remained within normal limits and all horses recovered successfully, most standing within 1 h of ceasing anaesthesia. There were no significant differences between groups in any variable except post operative pain when scores (simple descriptive scale) between 3 and 6 h were significantly lower after buprenorphine than after butorphanol. CONCLUSIONS: Horses experienced less post operative pain after buprenorphine than after butorphanol premedication. Compared with butorphanol, buprenorphine did not cause any different effects on vital function
Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the -network
Semiconductor glasses exhibit many unique optical and electronic anomalies.
We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508
(2010)) in which several of these anomalies arise from deep midgap electronic
states residing on high-strain regions intrinsic to the activated transport
above the glass transition. Here we demonstrate at the molecular level how this
scenario is realized in an important class of semiconductor glasses, namely
chalcogen and pnictogen containing alloys. Both the glass itself and the
intrinsic electronic midgap states emerge as a result of the formation of a
network composed of -bonded atomic -orbitals that are only weakly
hybridized. Despite a large number of weak bonds, these -networks are
stable with respect to competing types of bonding, while exhibiting a high
degree of structural degeneracy. The stability is rationalized with the help of
a hereby proposed structural model, by which -networks are
symmetry-broken and distorted versions of a high symmetry structure. The latter
structure exhibits exact octahedral coordination and is fully
covalently-bonded. The present approach provides a microscopic route to a fully
consistent description of the electronic and structural excitations in vitreous
semiconductors.Comment: 22 pages, 17 figures, revised version, final version to appear in J.
Chem. Phy
An investigation of mechanical nociceptive thresholds in dogs with hind limb joint pain compared to healthy control dogs
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