X-Ray absorption spectroscopy of H3O.

We report the X-ray absorption of isolated H3O+ cations at the O 1s edge. The molecular ions were prepared in a flowing afterglow ion source which was designed for the production of small water clusters, protonated water clusters, and hydrated ions. Isolated H2O+ cations have been analyzed for comparison. The spectra show significant differences in resonance energies and widths compared to neutral H2O with resonances shifting to higher energies by as much as 10 eV and resonance widths increasing by as much as a factor of 5. The experimental results are supported by time-dependent density functional theory calculations performed for both molecular cations, showing a good agreement with the experimental data. The spectra reported here could enable the identification of the individual molecules in charged small water clusters or liquid water using X-ray absorption spectroscopy.

Absorption spectra at the iodine 3d ionisation threshold following the CHxI+ (x = 0-3) cation sequence.

Yields of atomic iodine Iq+ (q≥ 2) fragments resulting from photoexcitation and photoionisation of the target cations CHxI+ (x = 0-3) have been measured in the photon-energy range 610 eV to 670 eV, which comprises the threshold for iodine 3d ionisation. The measured ion-yield spectra show two strong and broad resonance features due to the excitation of the 3d3/2,5/2 electrons into εf states similar to atomic iodine. In the 3d pre-edge range, electrons are excited into molecular orbitals consisting of iodine, carbon, and hydrogen atomic orbitals. These transitions have been identified by comparison with literature data and by simulations using time-dependent density functional theory (TDDFT) with the KMLYP functional. The ion-yield spectrum for CH3I+ resembles the spectrum of IH+ [Klumpp et al., Phys. Rev. A, 2018, 97, 033401] because the highest occupied molecular orbitals (HOMO) of the H and CH3 fragments both contain a single vacancy, only. For the molecular cations with higher number of vacancies in the valence molecular orbitals CHxI+ (x = 0-2), a stronger hybridisation of the molecular orbitals occurs between the organic fragment and the iodine resulting in a change of bonding from a single σ bond in CH3I+ to a triple bond including two π orbitals in CI+. This is reflected in the resonance energies of the observed absorption lines below the iodine 3d excitation threshold.

Inner-shell X-ray absorption spectra of the cationic series NHy+ (y = 0-3).

Ion yields following X-ray absorption of the cationic series NHy+ (y = 0-3) were measured to identify the characteristic absorption resonances in the energy range of the atomic nitrogen K-edge. Significant changes in the position of the absorption resonances were observed depending on the number of hydrogen atoms bound to the central nitrogen atom. Configuration interaction (CI) calculations were performed to obtain line assignments in the frame of molecular group theory. To validate the calculations, our assignment for the atomic cation N+, measured as a reference, was compared with published theoretical and experimental data.

The synchrotron radiation source PETRA III and its future ultra-low-emittance upgrade PETRA IV.

PETRA III at DESY is one of the brightest synchrotron radiation sources worldwide. It serves a broad international multidisciplinary user community from academia to industry at currently 25 specialised beamlines. With a storage-ring energy of 6 GeV, it provides mainly hard to high-energy X-rays for versatile experiments in a very broad range of scientific fields. It is ideally suited for an upgrade to the ultra-low emittance source PETRA IV, owing to its large circumference of 2304 m. With a targeted storage ring emittance of 20 × 5 pm 2 rad 2 , PETRA IV will reach spectral brightnesses two to three orders of magnitude higher than today. The unique beam parameters will make PETRA IV the ultimate in situ 3D microscope for biological, chemical, and physical processes helping to address key questions in health, energy, mobility, information technology, and earth and environment.

Suppression of X-ray-Induced Radiation Damage to Biomolecules in Aqueous Environments by Immediate Intermolecular Decay of Inner-Shell Vacancies.

The predominant reason for the damaging power of high-energy radiation is multiple ionization of a molecule, either direct or via the decay of highly excited intermediates, as, e.g., in the case of X-ray irradiation. Consequently, the molecule is irreparably damaged by the subsequent fragmentation in a Coulomb explosion. In an aqueous environment, however, it has been observed that irradiated molecules may be saved from fragmentation presumably by charge and energy dissipation mechanisms. Here, we show that the protective effect of the environment sets in even earlier than hitherto expected, namely immediately after single inner-shell ionization. By combining coincidence measurements of the fragmentation of X-ray-irradiated microsolvated pyrimidine molecules with theoretical calculations, we identify direct intermolecular electronic decay as the protective mechanism, outrunning the usually dominant Auger decay. Our results demonstrate that such processes play a key role in charge delocalization and have to be considered in investigations and models on high-energy radiation damage in realistic environments.

The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy.

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX+ at the cobalt L3-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX+ is in a 3A2g triplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.

Evaluation of the volumes of cranial cavities in Cavalier King Charles Spaniels with Chiari-like malformation and other brachycephalic dogs as measured via computed tomography.

OBJECTIVE-To measure the absolute and relative volumes of cranial vaults of Cavalier King Charles Spaniels (CKCSs) and other brachycephalic dogs for the purpose of evaluating a possible association between the volume of the caudal fossa (fossa caudalis cerebri; CF) and existence of Chiari-like malformation (CLM) and syringohydromyelia in CKCSs. ANIMALS-40 CKCSs and 25 brachycephalic dogs. PROCEDURES-The intracranial vault of all dogs was evaluated via computed tomography followed by magnetic resonance imaging. Volumes of the CF and the rostral and medial fossa (fossa rostralis et medialis cerebri) were determined. The ratio of the absolute volumes was calculated as the volume index (VI). RESULTS-All CKCSs had cranial characteristics consistent with CLM. There were no significant differences between CKCSs and brachycephalic dogs with respect to the VI and absolute volumes of the CF and rostral and medial fossas. The CKCSs without syringohydromyelia (n = 26) had a median VI of 0.1842, and CKCSs with syringohydromyelia (14) had a median VI of 0.1805. The median VI of other brachycephalic dogs was 0.1864. The VI did not differ among these 3 groups. CONCLUSIONS AND CLINICAL RELEVANCE-Results of this study suggested that descent of the cerebellum into the foramen magnum and the presence of syringohydromyelia in CKCSs are not necessarily associated with a volume reduction in the CF of the skull.

Hemodynamic instability induced by superselective angiography of the ophthalmic artery.

Retinoblastoma is one of the most common ophthalmic neoplasms affecting children worldwide. Since its recent introduction, superselective ophthalmic artery injection of chemotherapy with melphalan has significantly reduced the need for enucleation in patients with advanced disease and also shown to have minimal adverse effects on visual acuity as compared to the conventional therapy. Although no severe complications resulting in strokes or deaths have been reported, this treatment modality is not without difficulties. In this case discussion, we describe an event that has occurred to several pediatric patients undergoing superselective angiography of the ophthalmic artery that may be due to an oculopulmonary type reflex causing significant hemodynamic instability and hypoxemia.

Skeletal morphology and morphometry of the lumbosacral junction in German shepherd dogs and an evaluation of the possible genetic basis for radiographic findings.

The aim of this study was to identify skeletal variations in the lumbosacral junction (LSJ) of the German shepherd dog (GSD) compared with other large breeds. The radiographic traits of the LSJ were investigated in a group of 733 GSDs and a control group of 334 dogs of other breeds that were matched in terms of size. Nine morphological and 17 morphometric traits were recorded and analysed. Furthermore, the possibility of a genetic basis for these radiographic features was evaluated by calculation of genetic variance components. Five of the morphological and 14 of the morphometric traits varied significantly between the GSD group and the control group (P<0.05). Osteochondrosis of the sacral endplate (SOC) had a higher prevalence in the GSDs (10.1%) compared with controls (5.7%). The majority of LSJ degenerative changes recorded from the radiographs occurred in the GSDs. The extent and relative proportion of lumbosacral step formations were greater in the GSD group compared with controls (P<0.001). The lumbosacral vertebral canal height was reduced in the GSD compared with the control dogs (P<0.001) suggesting a primary stenosis. This was accentuated by an abrupt tapering of the vertebral canal at the level of the LSJ indicated by a lumbosacral ratio of 1.51 in the GSD. The skeletal morphology and morphometry of the LSJ in the GSD seem to be different from that found in other large dogs. For multiple traits frequently observed in GSD such as SOC, step formations, and LSJ stenosis, moderate to high non-zero heritabilities were noted. As these features are also assumed to promote lumbosacral disease, selection against these traits is suggested.

Porencephaly in dogs and cats: magnetic resonance imaging findings and clinical signs.

Magnetic resonance imaging (MRI) features of brain lesions in 5 dogs and 2 cats characterized by extensive cystic changes of the cerebral hemispheres in terms of a porencephaly are presented. Age at diagnosis ranged from 12 weeks to 7 years. MRI findings were confined to the forebrain. Porencephalic lesions appeared as wedge-shaped parenchymal defects connecting the ventricular system and the subarachnoid space or as large cystic defects in the cerebral hemispheres. Although in two adult dogs the porencephalic lesions were asymptomatic, the other animals showed clinical symptoms depending on the affected cerebral area. Three animals had seizures. Interestingly, four animals showed neurological signs normally not localized to the forebrain (nystagmus, hypermetria, ataxia). Whether these clinical signs are related to impaired function of the cerebral cortex or to not recognizable lesions in the cerebello-vestibular system could not be further clarified. Although the defects develop intrauterine or postnatal, the clinical symptoms can occur later in life. The definition of porencephaly as well as its subclassification is not uniform in veterinary medicine. We suggest the term encephaloclastic porencephaly unregarding the underlying cause of the defect, which cannot be further specified by diagnostic imaging.