584 research outputs found
The heats of formation of the haloacetylenes XCCY [X, Y = H, F, Cl]: basis set limit ab initio results and thermochemical analysis
The heats of formation of haloacetylenes are evaluated using the recent W1
and W2 ab initio computational thermochemistry methods. These calculations
involve CCSD and CCSD(T) coupled cluster methods, basis sets of up to spdfgh
quality, extrapolations to the one-particle basis set limit, and contributions
of inner-shell correlation, scalar relativistic effects, and (where relevant)
first-order spin-orbit coupling. The heats of formation determined using W2
theory are: \hof(HCCH) = 54.48 kcal/mol, \hof(HCCF) = 25.15 kcal/mol,
\hof(FCCF) = 1.38 kcal/mol, \hof(HCCCl) = 54.83 kcal/mol, \hof(ClCCCl) = 56.21
kcal/mol, and \hof(FCCCl) = 28.47 kcal/mol. Enthalpies of hydrogenation and
destabilization energies relative to acetylene were obtained at the W1 level of
theory. So doing we find the following destabilization order for acetylenes:
FCCF ClCCF HCCF ClCCCl HCCCl HCCH. By a combination of W1
theory and isodesmic reactions, we show that the generally accepted heat of
formation of 1,2-dichloroethane should be revised to -31.80.6 kcal/mol, in
excellent agreement with a very recent critically evaluated review. The
performance of compound thermochemistry schemes such as G2, G3, G3X and CBS-QB3
theories has been analyzed.Comment: Mol. Phys., in press (E. R. Davidson issue
A Process for Co-Designing Educational Technology Systems for Refugee Children
There is a growing interest in the potential for technology to facilitate emergency education of refugee children. However, designing in this space requires knowledge of the displaced population and the contextual dynamics surrounding it. Design should therefore be informed by both existing research across relevant disciplines, and from the practical experience of those who are on the ground facing the problem in real life. This paper describes a process for designing appropriate technology for these settings. The process draws on literature from emergency education, student engagement and motivation, educational technology, and participatory design. We emphasise a thorough understanding of the problem definition, the nature of the emergency, and of socio-cultural aspects that can inform the design process. We describe how this process was implemented leading to the design of a digital learning space for children living in a refugee camp in Greece. This drew on involving different groups of participants such as social-workers, parents, and children
A selected ion flow tube study of the ion-molecule reactions of monochloroethene, trichloroethene and tetrachloroethene
Data for the rate coefficients and product cations of the reactions of a large number of atomic and small molecular cations with monochloroethene, trichloroethene and tetrachloroethene in a selected ion flow tube at 298 K are reported. The recombination energy of the ions range from 6.27 eV (HO) through to 21.56 eV (Ne). Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental values. Thermochemistry and mass balance predict the most feasible neutral products. Together with previously reported results for the three isomers of dichloroethene (J. Phys. Chem. A., 2006, 110, 5760), the fragment ion branching ratios have been compared with those from threshold photoelectron photoion coincidence spectroscopy over the photon energy range 9-22 eV to determine the importance or otherwise of long-range charge transfer. For ions with recombination energy in excess of the ionisation energy of the chloroethene, charge transfer is energetically allowed. The similarity of the branching ratios from the two experiments suggest that long-range charge transfer is dominant. For ions with recombination energy less than the ionisation energy, charge transfer is not allowed; chemical reaction can only occur following formation of an ion-molecule complex, where steric effects are more significant. The products that are now formed and their percentage yield is a complex interplay between the number and position of the chlorine atoms with respect to the C=C bond, where inductive and conjugation effects can be important
Phonon Emission from a 2D Electron Gas: Evidence of Transition to the Hydrodynamic Regime
Using as a thermometer the temperature dependent magneto-transport of a
two-dimensional electron gas, we find that effective temperature scales with
current as , where in the {\it Shubnikov
de-Haas} regime, and in both the {\it integer and fractional}
quantum Hall effect. This implies the phonon energy emission rate changes from
the expected to . We explain this, as well as the
dramatic enhancement in phonon emission efficiency using a hydrodynamic model.Comment: 4 pages, 2 Postscript figures uuencoded with TeX file uses psfig
macro. Submitted to Phys. Rev. Let
Vitamin D deficiency is associated with IL-6 levels and monocyte activation in HIV-infected persons
Immune activation plays a key role in HIV pathogenesis. Markers of inflammation have been associated with vitamin D deficiency in the general population. Studies have also demonstrated associations of vitamin D deficiency with increased risk of HIV progression and death. The relationship between persistent inflammation and immune activation during chronic HIV infection and vitamin D deficiency remains unclear.Cryopreserved specimens were analyzed from 663 participants at the time of enrollment from the Study to Understand the Natural History of HIV/AIDS in the Era of Effective Therapy (SUN Study) from 2004 to 2006. Biomarkers of inflammation, atherosclerosis, and coagulation were measured using enzyme-linked immunosorbent assays (ELISAs) and electrochemiluminescence. 25(OH)D, the stable precursor form of vitamin D, was measured using a radioimmunoassay with levels defined as: normal (â„30ng/mL), insufficient (20-29 ng/mL) and deficient (<20 ng/mL). Monocyte phenotypes were assessed by flow cytometry. Linear and logistic regression models were used to determine statistical associations between biomarkers and vitamin D deficiency.25(OH)D levels were deficient in 251 (38%) participants, insufficient in 222 (34%), and normal in 190 (29%). Patients with vitamin D deficiency, when compared to those with insufficient or normal vitamin D levels, had increased levels of IL-6 (23%; p<0.01), TNF-α (21%, p = 0.03), D-dimer (24%, p = 0.01), higher proportions of CD14dimCD16+ (22%, p<0.01) and CX3CR1+ monocytes (48%; p<0.001) and decreased frequency of CCR2+ monocytes (-3.4%, p<0.001). In fully adjusted models, vitamin D associations with abnormal biomarker levels persisted for IL-6 levels and CX3CR1+ and CCR2+ phenotypes.Vitamin D deficiency is associated with greater inflammation and activated monocyte phenotypes. The role of vitamin D deficiency in persistent immune activation and associated complications during chronic HIV disease should be further evaluated as a possible target for intervention
Molecular dissection of box jellyfish venom cytotoxicity highlights an effective venom antidote
The box jellyfish Chironex fleckeri is extremely venomous, and envenoming causes tissue
necrosis, extreme pain and death within minutes after severe exposure. Despite rapid and
potent venom action, basic mechanistic insight is lacking. Here we perform molecular dissection
of a jellyfish venom-induced cell death pathway by screening for host components
required for venom exposure-induced cell death using genome-scale lenti-CRISPR mutagenesis.
We identify the peripheral membrane protein ATP2B1, a calcium transporting
ATPase, as one host factor required for venom cytotoxicity. Targeting ATP2B1 prevents
venom action and confers long lasting protection. Informatics analysis of host genes required
for venom cytotoxicity reveal pathways not previously implicated in cell death. We also
discover a venom antidote that functions up to 15 minutes after exposure and suppresses
tissue necrosis and pain in mice. These results highlight the power of whole genome CRISPR
screening to investigate venom mechanisms of action and to rapidly identify new medicines
A Halomethane thermochemical network from iPEPICO experiments and quantum chemical calculations
Internal energy selected halomethane cations CH3Cl+, CH2Cl2+, CHCl3+, CH3F+, CH2F2+, CHClF2+ and CBrClF2+ were prepared by vacuum ultraviolet photoionization, and their lowest energy dissociation channel studied using imaging photoelectron photoion coincidence spectroscopy (iPEPICO). This channel involves hydrogen atom loss for CH3F+, CH2F2+ and CH3Cl+, chlorine atom loss for CH2Cl2+, CHCl3+ and CHClF2+, and bromine atom loss for CBrClF2+. Accurate 0 K appearance energies, in conjunction with ab initio isodesmic and halogen exchange reaction energies, establish a thermochemical network, which is optimized to update and confirm the enthalpies of formation of the sample molecules and their dissociative photoionization products. The ground electronic states of CHCl3+, CHClF2+ and CBrClF2+ do not confirm to the deep well assumption, and the experimental breakdown curve deviates from the deep well model at low energies. Breakdown curve analysis of such shallow well systems supplies a satisfactorily succinct route to the adiabatic ionization energy of the parent molecule, particularly if the threshold photoelectron spectrum is not resolved and a purely computational route is unfeasible. The ionization energies have been found to be 11.47 ± 0.01 eV, 12.30 ± 0.02 eV and 11.23 ± 0.03 eV for CHCl3, CHClF2 and CBrClF2, respectively. The updated 0 K enthalpies of formation, âfHo0K(g) for the ions CH2F+, CHF2+, CHCl2+, CCl3+, CCl2F+ and CClF2+ have been derived to be 844.4 ± 2.1, 601.6 ± 2.7, 890.3 ± 2.2, 849.8 ± 3.2, 701.2 ± 3.3 and 552.2 ± 3.4 kJ molâ1, respectively. The âfHo0K(g) values for the neutrals CCl4, CBrClF2, CClF3, CCl2F2 and CCl3F and have been determined to be â94.0 ± 3.2, â446.6 ± 2.7, â702.1 ± 3.5, â487.8 ± 3.4 and â285.2 ± 3.2 kJ molâ1, respectively
meson production in Au collisions at GeV
The PHENIX experiment has measured meson production in Au
collisions at GeV using the dimuon and dielectron decay
channels. The meson is measured in the forward (backward) -going
(Au-going) direction, () in the transverse-momentum
() range from 1--7 GeV/, and at midrapidity in the
range below 7 GeV/. The meson invariant yields and
nuclear-modification factors as a function of , rapidity, and centrality
are reported. An enhancement of meson production is observed in the
Au-going direction, while suppression is seen in the -going direction, and
no modification is observed at midrapidity relative to the yield in
collisions scaled by the number of binary collisions. Similar behavior was
previously observed for inclusive charged hadrons and open heavy flavor
indicating similar cold-nuclear-matter effects.Comment: 484 authors, 16 pages, 12 figures, 6 tables. v1 is the version
accepted for publication in Phys. Rev. C. Data tables for the points plotted
in the figures are given in the paper itsel
Measurements of double-helicity asymmetries in inclusive production in longitudinally polarized collisions at GeV
We report the double helicity asymmetry, , in inclusive
production at forward rapidity as a function of transverse momentum
and rapidity . The data analyzed were taken during
GeV longitudinally polarized collisions at the Relativistic Heavy Ion
Collider (RHIC) in the 2013 run using the PHENIX detector. At this collision
energy, particles are predominantly produced through gluon-gluon
scatterings, thus is sensitive to the gluon polarization
inside the proton. We measured by detecting the decay
daughter muon pairs within the PHENIX muon spectrometers in the
rapidity range . In this kinematic range, we measured the
to be ~(stat)~~(syst). The
can be expressed to be proportional to the product of the
gluon polarization distributions at two distinct ranges of Bjorken : one at
moderate range where recent RHIC data of jet and
double helicity spin asymmetries have shown evidence for significant gluon
polarization, and the other one covering the poorly known small- region . Thus our new results could be used to further
constrain the gluon polarization for .Comment: 335 authors, 10 pages, 4 figures, 3 tables, 2013 data. Version
accepted for publication by Phys. Rev. D. Plain text data tables for the
points plotted in figures for this and previous PHENIX publications are (or
will be) publicly available at http://www.phenix.bnl.gov/papers.htm
- âŠ