561 research outputs found
The structure and energetics of He and He nanodroplets doped with alkaline earth atoms
We present systematic results, based on density functional calculations, for
the structure and energetics of He and He nanodroplets doped with
alkaline earth atoms. We predict that alkaline earth atoms from Mg to Ba go to
the center of He drops, whereas Ca, Sr, and Ba reside in a deep dimple at
the surface of He drops, and Mg is at their center. For Ca and Sr, the
structure of the dimples is shown to be very sensitive to the He-alkaline earth
pair potentials used in the calculations. The transition
of strontium atoms attached to helium nanodroplets of either isotope has been
probed in absorption experiments. The spectra show that strontium is solvated
inside He nanodroplets, supporting the calculations. In the light of our
findings, we emphasize the relevance of the heavier alkaline earth atoms for
analyzing mixed He-He nanodroplets, and in particular, we suggest their
use to experimentally probe the He-He interface.Comment: Typeset using Revtex, 20 pages and 8 Postscript file
Characterisation of the local mechanical properties of atherosclerotic plaque tissue using an indentation test
Visible photodissociation spectroscopy of PAH cations and derivatives in the PIRENEA experiment
The electronic spectra of gas-phase cationic polycyclic aromatic hydrocarbons
(PAHs), trapped in the Fourier Transform Ion Cyclotron Resonance cell of the
PIRENEA experiment, have been measured by multiphoton dissociation spectroscopy
in the 430-480 nm spectral range using the radiation of a mid-band optical
parametric oscillator laser. We present here the spectra recorded for different
species of increasing size, namely the pyrene cation (C16H10+), the
1-methylpyrene cation (CH3-C16H9+), the coronene cation (C24H12+), and its
dehydrogenated derivative C24H10+. The experimental results are interpreted
with the help of time-dependent density functional theory calculations and
analysed using spectral information on the same species obtained from matrix
isolation spectroscopy data. A kinetic Monte Carlo code has also been used, in
the case of pyrene and coronene cations, to estimate the absorption
cross-sections of the measured electronic transitions. Gas-phase spectra of
highly reactive species such as dehydrogenated PAH cations are reported for the
first time
Infrared Multiple-Photon Dissociation Action Spectroscopy of the b(2)(+) Ion from PPG: Evidence of Third Residue Affecting b(2)(+) Fragment Structure
Infrared multiple-photon dissociation (IRMPD) action spectroscopy was performed on the b2 + fragment ion from the protonated PPG tripeptide. Comparison of the experimental infrared spectrum with computed spectra for both oxazolone and diketopiperazine structures indicates that the majority of the fragment ion population has an oxazolone structure with the remainder having a diketopiperazine structure. This result is in contrast with a recent study of the IRMPD action spectrum of the PP b2 + fragment ion from PPP, which was found to be nearly 100% diketopiperazine (Martens et al. Int. J. Mass Spectrom. 2015, 377, 179). The diketopiperazine b2 + ion is thermodynamically more stable than the oxazolone but normally requires a trans/cis peptide bond isomerization in the dissociating peptide. Martens et al. showed through IRMPD action spectroscopy that the PPP precursor ion was in a conformation in which the first peptide bond is already in the cis conformation and thus it was energetically favorable to form the thermodynamically-favored diketopiperazine b2 + ion. In the present case, solution-phase NMR spectroscopy and gas-phase IRMPD action spectroscopy show that the PPGprecursor ion has its first amide bond in a trans configuration suggesting that the third residue is playing an important role in both the structure of the peptide and the associated ring-closure barriers for oxazolone and diketopiperazine formation
The 5.25 & 5.7 m Astronomical Polycyclic Aromatic Hydrocarbon Emission Features
Astronomical mid-IR spectra show two minor PAH features at 5.25 and 5.7
m (1905 and 1754 cm) that hitherto have been little studied,
but contain information about the astronomical PAH population that complements
that of the major emission bands. Here we report a study involving both
laboratory and theoretical analysis of the fundamentals of PAH spectroscopy
that produce features in this region and use these to analyze the astronomical
spectra. The ISO SWS spectra of fifteen objects showing these PAH features were
considered for this study, of which four have sufficient S/N between 5 and 6
m to allow for an in-depth analysis. All four astronomical spectra show
similar peak positions and profiles. The 5.25 m feature is peaked and
asymmetric, while the 5.7 m feature is broader and flatter. Detailed
analysis of the laboratory spectra and quantum chemical calculations show that
the astronomical 5.25 and 5.7 m bands are a blend of combination,
difference and overtone bands primarily involving CH stretching and CH in-plane
and CH out-of-plane bending fundamental vibrations. The experimental and
computational spectra show that, of all the hydrogen adjacency classes possible
on PAHs, solo and duo hydrogens consistently produce prominent bands at the
observed positions whereas quartet hydrogens do not. In all, this a study
supports the picture that astronomical PAHs are large with compact, regular
structures. From the coupling with primarily strong CH out-of-plane bending
modes one might surmise that the 5.25 and 5.7 m bands track the neutral
PAH population. However, theory suggests the role of charge in these
astronomical bands might also be important.Comment: Accepted ApJ, 40 pages in pre-print, 14 figures, two onlin
IRMPD spectroscopy sheds new (InfraRed) light on the sulfate pattern of carbohydrates
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Exponentially growing tearing modes in Rijnhuizen Tokamak Project plasmas
The local measurement of the island width w, around the resonant surface, allowed a direct test of the extended Rutherford model [P. H. Rutherford, PPPL Report-2277 (1985)], describing the evolution of radiation-induced tearing modes prior to disruptions of tokamak plasmas. It is found that this model accounts very well for the observed exponential growth and supports radiation losses as being the main driving mechanism. The model implies that the effective perpendicular electron heat conductivity in the island is smaller than the global one. Comparison of the local measurements of w with the magnetic perturbed field showed that w1/2 was valid for widths up to 18% of the minor radius
3D Fiber Orientation in Atherosclerotic Carotid Plaques
Atherosclerotic plaque rupture is the primary trigger of fatal cardiovascular events. Fibrillar collagen in atherosclerotic plaques and their directionality are anticipated to play a crucial role in plaque rupture. This study aimed assessing 3D fiber orientations and architecture in atherosclerotic plaques for the first time.Seven carotid plaques were imaged ex-vivo with a state-of-the-art Diffusion Tensor Imaging (DTI) technique, using a high magnetic field (9.4. Tesla) MRI scanner. A 3D spin-echo sequence with uni-polar diffusion sensitizing pulsed field gradients was utilized for DTI and fiber directions were assessed from diffusion tensor measurements. The distribution of the 3D fiber orientations in atherosclerotic plaques were quantified and the principal fiber orientations (circumferential, longitudinal or radial) were determined.Overall, 52% of the fiber orientations in the carotid plaque specimens were closest to the circumferential direction, 34% to the longitudinal direction, and 14% to the radial direction. Statistically no significant difference was measured in the amount of the fiber orientations between the concentric and eccentric plaque sites. However, concentric plaque sites showed a distinct structural organization, where the principally longitudinally oriented fibers were closer to the luminal side and the principally circumferentially oriented fibers were located more abluminally. The acquired unique information on 3D plaque fiber direction will help understanding pathobiological mechanisms of atherosclerotic plaque progression and pave the road to more realistic biomechanical plaque modeling for rupture assessment
Estimated IR and phosphorescence emission fluxes for specific Polycyclic Aromatic Hydrocarbons in the Red Rectangle
Following the tentative identification of the blue luminescence in the Red
Rectangle by Vijh et al. (2005), we compute absolute fluxes for the vibrational
IR emission and phosphorescence bands of three small polycyclic aromatic
hydrocarbons. The calculated IR spectra are compared with available ISO
observations. A subset of the emission bands are predicted to be observable
using presently available facilities, and can be used for an immediate,
independent, discriminating test on their alleged presence in this well-known
astronomical object.Comment: accepted for publication on A&
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