The 5.25 & 5.7 μ\mum Astronomical Polycyclic Aromatic Hydrocarbon Emission Features

Astronomical mid-IR spectra show two minor PAH features at 5.25 and 5.7 $\mu$m (1905 and 1754 cm$^{\rm - 1}$) 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 $\mu$m to allow for an in-depth analysis. All four astronomical spectra show similar peak positions and profiles. The 5.25 $\mu$m feature is peaked and asymmetric, while the 5.7 $\mu$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 $\mu$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 $\mu$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

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

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

High resolution temperature and density profiles during the energy quench of density limit disruptions in Rijnhuizen tokamak project

Measurements of the electron temperature, Te, and density, ne, during the energy quench of a major disruption showed that the onset of Te erosion in the neighborhood of the m/n = 2/1 O point at the low field side (LFS) accelerates the well-known m/n = 1/1 erosion of the core temperature. During this phase Te(r) is only partially flat in the region between the q = 2 and the q = 1 surfaces and ne(r) decreases in the core and increases inside the m/n = 2/1 island. Immediately after the flattening of Te(r) a large peak in Te and to a lesser extent in ne has been observed. This peak is radially localized at the q = 2 radius at the LFS, is very short lived and is poloidally asymmetric. Te profiles measured by the heterodyne radiometer and the Thomson scattering agree very well up to the time Te(r) flattens but afterwards can be a factor of two different

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

Probing the competition among different coordination motifs in metal-ciprofloxacin complexes through IRMPD spectroscopy and DFT calculations

The vibrational spectra of ciprofloxacin complexes with monovalent (Li+, Na+, K+, Ag+) and polyvalent (Mg2+, Al3+) metal ions are recorded in the range 1000-1900 cm(-1) by means of infrared multiple-photon dissociation (IRMPD) spectroscopy. The IRMPD spectra are analyzed and interpreted in the light of density functional theory (DFT)-based quantum chemical calculations in order to identify the possible structures present under our experimental conditions. For each metal-ciprofloxacin complex, four isomers are predicted, considering different chelation patterns. A good agreement is found between the measured IRMPD spectrum and the calculated absorption spectrum of the most stable isomer for each complex. Metal ion size and charge are found to drive the competition among the different coordination motifs: small size and high charge density metal ions prefer to coordinate the quinolone between the two carbonyl oxygen atoms, whereas large-size metal ions prefer the carboxylate group as a coordination site. In the latter case, an intramolecular hydrogen bond compensates the weaker interaction established by these cations. The role of the metal cation on the stabilization of ionic and nonionic structures of ciprofloxacin is also investigated. It is found that large-size metal ions preferentially stabilize charge separated motifs and that the increase of metal ion charge has a stabilizing effect on the zwitterionic form of ciprofloxacin

Spectroscopic Evidence for an Oxazolone Structure in Anionic b-Type Peptide Fragments

Infrared spectra of anionic b-type fragments generated by collision induced dissociation (CID) from deprotonated peptides are reported. Spectra of the b2 fragments of deprotonated AlaAlaAla and AlaTyrAla have been recorded over the 800–1800 cm–1 spectral range by multiple-photon dissociation (MPD) spectroscopy using an FTICR mass spectrometer in combination with the free electron laser FELIX. Structural characterization of the b-type fragments is accomplished by comparison with density functional theory calculated spectra at the B3LYP/6-31++G(d,p) level for different isomeric structures. Although diketopiperazine structures represent the energetically lowest isomers, the IR spectra suggest an oxazolone structure for the b2 fragments of both peptides. Deprotonation is shown to occur on the oxazolone α-carbon, which leads to a conjugated structure in which the negative charge is practically delocalized over the entire oxazolone ring, providing enhanced gas-phase stability

Coupled Blind Signal Separation and Spectroscopic Database Fitting of the Mid Infrared PAH Features

The aromatic infrared bands (AIBs) observed in the mid infrared spectrum are attributed to Polycyclic Aromatic Hydrocarbons (PAHs). We observe the NGC 7023-North West (NW) PDR in the mid-infrared (10 - 19.5 micron) using the Infrared Spectrometer (IRS), on board Spitzer. Clear variations are observed in the spectra, most notably the ratio of the 11.0 to 11.2 micron bands, the peak position of the 11.2 and 12.0 micron bands, and the degree of asymmetry of the 11.2 micron band. The observed variations appear to change as a function of position within the PDR. We aim to explain these variations by a change in the abundances of the emitting components of the PDR. A Blind Signal Separation (BSS) method, i.e. a Non-Negative Matrix Factorization algorithm is applied to separate the observed spectrum into components. Using the NASA Ames PAH IR Spectroscopic Database, these extracted signals are fit. The observed signals alone were also fit using the database and these components are compared to the BSS components. Three component signals were extracted from the observation using BSS. We attribute the three signals to ionized PAHs, neutral PAHs, and Very Small Grains (VSGs). The fit of the BSS extracted spectra with the PAH database further confirms the attribution to ionized and neutral PAHs and provides confidence in both methods for producing reliable results. The 11.0 micron feature is attributed to PAH cations while the 11.2 micron band is attributed to neutral PAHs. The VSG signal shows a characteristically asymmetric broad feature at 11.3 micron with an extended red wing. By combining the NASA Ames PAH IR Spectroscopic Database fit with the BSS method, the independent results of each method can be confirmed and some limitations of each method are overcome