Portal venous gas after a failed endoscopic retrograde cholangiopancreatography attempt in a patient with a large hepatocellular carcinoma: A case report

The cause of hepatic portal vein gas (HPVG) is variable. Good knowledge of the possible causes, combined with the clinical assessment of the patient and a good quality imaging, is required to correctly identify the underlying cause of HPVG and to best predict the prognosis

High resolution NEXAFS of perylene and PTCDI : a surface science approach to molecular orbital analysis

We made use of synchrotron radiation to perform near edge X-ray absorption fine structure spectroscopy, NEXAFS, at the carbon K-edge of perylene and perylene-tetracarboxylic-diimide, PTCDI. Reference spectra measured for isolated molecules in the gas phase are compared with polarization dependent NEXAFS spectra measured on highly oriented thin films in order to study the symmetry of the molecular orbitals. The molecular overlayers are grown onto the rutile TiO2(110) surface for which the large anisotropic corrugation effectively drives the molecular orientation, while its dielectric nature prevents the rehybridization of the molecular orbitals. We employed density functional theory, DFT, calculations to disentangle the contribution of specific carbon atoms to the molecular density of states. Numerical simulations correctly predict the observed NEXAFS azimuthal dichroism of the \u3c3* resonances above the ionization threshold, from which we determine the full geometric orientation of the overlayer molecules. A discrepancy observed for the spectral contribution of the imide carbon atom to the calculated unoccupied molecular orbitals has been explained in terms of initial state effects, as determined by Hartree-Fock corrections and in full agreement with the corresponding shift of the C 1s core level measured by X-ray photoelectron spectroscopy, XPS. \ua9 the Partner Organisations 2014

Photoionization Dynamics of the Tetraoxo Complexes OsO4 and RuO4

The photoionization dynamics of OsO4 and RuO4, chosen as model systems of small-size mononuclear heavy-metal complexes, has been theoretically studied by the time-dependent density functional theory (TDDFT). Accurate experimental measurements of photoionization dynamics as a benchmarking test for the theory are reported for the photoelectron asymmetry parameters of outer valence ionizations of OsO4, measured in the 17-90 eV photon energy range. The theoretical results are in good agreement with the available experimental data. The observed dynamical behavior of partial cross sections and asymmetry parameters has been related to both the coupling to the continuum of discrete excited states, giving strong modulations in the photon energy dependency, and the atomic composition of the initial ionized states, which determines the rate of decay of ionization probability for increasing excitation energies. Overall, an extensive analysis of the photoionization dynamics for valence and core orbitals is presented, showing good agreement with all the available experimental data. This provides confidence for the validity of the TDDFT approach in describing photoionization of heavy transition element compounds, with the perspective of being used for larger systems. Further experimental work is suggested for RuO4 to gather evidence of the sensitivity of the theoretical method to the nature of the metal atom

O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon?photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core?valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300?650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400?500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon?photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2+. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV?O+ coincidence peak in the mass spectrum carries some information on the initial core excitatio

A public early intervention approach to first-episode psychosis: Treated incidence over 7 years in the Emilia-Romagna region

AimTo estimate the treated incidence of individuals with first-episode psychosis (FEP) who contacted the Emilia-Romagna public mental healthcare system (Italy); to examine the variability of incidence and user characteristics across centres and years. MethodsWe computed the raw treated incidence in 2013-2019, based on FEP users aged 18-35, seen within or outside the regional program for FEP. We modelled FEP incidence across 10 catchment areas and 7 years using Bayesian Poisson and Negative Binomial Generalized Linear Models of varying complexity. We explored associations between user characteristics, study centre and year comparing variables and socioclinical clusters of subjects. ResultsThousand three hundred and eighteen individuals were treated for FEP (raw incidence: 25.3 / 100.000 inhabitant year, IQR: 15.3). A Negative Binomial location-scale model with area, population density and year as predictors found that incidence and its variability changed across centres (Bologna: 36.55; 95% CrI: 30.39-43.86; Imola: 3.07; 95% CrI: 1.61-4.99) but did not follow linear temporal trends or density. Centers were associated with different user age, gender, migrant status, occupation, living conditions and cluster distribution. Year was associated negatively with HoNOS score (R = -0.09, p < .001), duration of untreated psychosis (R = -0.12, p < .001) and referral type. ConclusionsThe Emilia-Romagna region presents a relatively high but variable incidence of FEP across areas, but not in time. More granular information on social, ethnic and cultural factors may increase the level of explanation and prediction of FEP incidence and characteristics, shedding light on social and healthcare factors influencing FEP

The Low Density Matter (LDM) beamline at FERMI: Optical layout and first commissioning

The Low Density Matter (LDM) beamline has been built as part of the FERMI free-electron laser (FEL) facility to serve the atomic, molecular and cluster physics community. After the commissioning phase, it received the first external users at the end of 2012. The design and characterization of the LDM photon transport system is described, detailing the optical components of the beamline

Untangling the chemical evolution of Titan's atmosphere and surface–from homogeneous to heterogeneous chemistry

The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further the similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date

Interatomic Coulombic Decay Processes after Multiple Valence Excitations in Ne Clusters

We present a comprehensive analysis of autoionization processes in Ne clusters (~5000 atoms) after multiple valence excitations by free electron laser radiation. The evolution from 2-body interatomic Coulombic decay (ICD) to 3-body ICD is demonstrated when changing from surface to bulk Frenkel exciton excitation. Super Coster-Kronig type 2-body ICD is observed at Wannier exciton which quenches the main ICD channel