477 research outputs found
Strong electron correlations in cobalt valence tautomers
We have examined cobalt based valence tautomer molecules such as
Co(SQ)(phen) using density functional theory (DFT) and variational
configuration interaction (VCI) approaches based upon a model Hamiltonian. Our
DFT results extend earlier work by finding a reduced total energy gap (order
0.6 eV) between high temperature and low temperature states when we fully relax
the coordinates (relative to experimental ones). Futhermore we demonstrate that
the charge transfer picture based upon formal valence arguments succeeds
qualitatively while failing quantitatively due to strong covalency between the
Co 3 orbitals and ligand orbitals. With the VCI approach, we argue that
the high temperature, high spin phase is strongly mixed valent, with about 30 %
admixture of Co(III) into the predominantly Co(II) ground state. We confirm
this mixed valence through a fit to the XANES spectra. Moreover, the strong
electron correlations of the mixed valent phase provide an energy lowering of
about 0.2-0.3 eV of the high temperature phase relative to the low temperature
one. Finally, we use the domain model to account for the extraordinarily large
entropy and enthalpy values associated with the transition.Comment: 10 pages, 4 figures, submitted to J. Chem. Phy
Unusual Electronic Features and Reactivity of the Dipyridylazaallyl Ligand: Characterizations of (smif) 2
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Intrathecal enzyme replacement for Hurler syndrome: biomarker association with neurocognitive outcomes.
PurposeAbnormalities in cerebrospinal fluid (CSF) have been reported in Hurler syndrome, a fatal neurodegenerative lysosomal disorder. While no biomarker has predicted neurocognitive response to treatment, one of these abnormalities, glycosaminoglycan nonreducing ends (NREs), holds promise to monitor therapeutic efficacy. A trial of intrathecal enzyme replacement therapy (ERT) added to standard treatment enabled tracking of CSF abnormalities, including NREs. We evaluated safety, biomarker response, and neurocognitive correlates of change.MethodsIn addition to intravenous ERT and hematopoietic cell transplantation, patients (N = 24) received intrathecal ERT at four peritransplant time points; CSF was evaluated at each point. Neurocognitive functioning was quantified at baseline, 1 year, and 2 years posttransplant. Changes in CSF biomarkers and neurocognitive function were evaluated for an association.ResultsOver treatment, there were significant decreases in CSF opening pressure, biomarkers of disease activity, and markers of inflammation. Percent decrease in NRE from pretreatment to final intrathecal dose posttransplant was positively associated with percent change in neurocognitive score from pretreatment to 2 years posttransplant.ConclusionIntrathecal ERT was safe and, in combination with standard treatment, was associated with reductions in CSF abnormalities. Critically, we report evidence of a link between a biomarker treatment response and neurocognitive outcome in Hurler syndrome
Properly Interpreting the Epidemiologic Evidence About the Health Effects of Industrial Wind Turbines on Nearby Residents
A Burgessian critique of nominalistic tendencies in contemporary mathematics and its historiography
We analyze the developments in mathematical rigor from the viewpoint of a
Burgessian critique of nominalistic reconstructions. We apply such a critique
to the reconstruction of infinitesimal analysis accomplished through the
efforts of Cantor, Dedekind, and Weierstrass; to the reconstruction of Cauchy's
foundational work associated with the work of Boyer and Grabiner; and to
Bishop's constructivist reconstruction of classical analysis. We examine the
effects of a nominalist disposition on historiography, teaching, and research.Comment: 57 pages; 3 figures. Corrected misprint
Quantification of radial arterial pulse characteristics change during exercise and recovery
It is physiologically important to understand the arterial pulse waveform characteristics change during exercise and recovery. However, there is a lack of a comprehensive investigation. This study aimed to provide scientific evidence on the arterial pulse characteristics change during exercise and recovery. Sixty-five healthy subjects were studied. The exercise loads were gradually increased from 0 to 125 W for female subjects and to 150 W for male subjects. Radial pulses were digitally recorded during exercise and 4-min recovery. Four parameters were extracted from the raw arterial pulse waveform, including the pulse amplitude, width, pulse peak and dicrotic notch time. Five parameters were extracted from the normalized radial pulse waveform, including the pulse peak and dicrotic notch position, pulse Area, Area1 and Area2 separated by notch point. With increasing loads during exercise, the raw pulse amplitude increased significantly with decreased pulse period, reduced peak and notch time. From the normalized pulses, the pulse Area, pulse Area1 and Area2 decreased, respectively, from 38 ± 4, 61 ± 5 and 23 ± 5 at rest to 34 ± 4, 52 ± 6 and 13 ± 5 at 150-W exercise load. During recovery, an opposite trend was observed. This study quantitatively demonstrated significant changes of radial pulse characteristics during different exercise loads and recovery phases
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