Core excitation in Ozone localized to one of two symmetry-equivalent chemical bonds - molecular alignment through vibronic coupling

Core excitation from terminal oxygen O$_T$ in O$_3$ is shown to be an excitation from a localized core orbital to a localized valence orbital. The valence orbital is localized to one of the two equivalent chemical bonds. We experimentally demonstrate this with the Auger Doppler effect which is observable when O$_3$ is core-excited to the highly dissociative O$_{T}$1s$^{-1}$7a$_1^1$ state. Auger electrons emitted from the atomic oxygen fragment carry information about the molecular orientation relative to the electromagnetic field vector at the moment of excitation. The data together with analytical functions for the electron-peak profiles give clear evidence that the preferred molecular orientation for excitation only depends on the orientation of one bond, not on the total molecular orientation. The localization of the valence orbital "7a$_1$" is caused by mixing of the valence orbital "5b$_2$" through vibronic coupling of anti-symmetric stretching mode with b$_2$-symmetry. To the best of our knowledge, it is the first discussion of the localization of a core excitation of O$_3$. This result explains the success of the widely used assumption of localized core excitation in adsorbates and large molecules

The population impact of common mental disorders and long-term physical conditions on disability and hospital admission

Background: Long-term physical conditions (LTCs) consume the largest share of healthcare budgets. Although common mental disorders (CMDs) and LTCs often co-occur, the potential impact of improved mental health treatment on severe disability and hospital admissions for physical health problems remains unknown. Method: A cross-sectional study of 7403 adults aged 16–95 years living in private households in England was performed. LTCs were ascertained by prompted self-report. CMDs were ascertained by structured clinical interview. Disability was assessed using questions about problems with activities of daily living. Population impact and potential preventive gain were estimated using population-attributable fraction (PAF), and conservative estimates were obtained using ‘treated non-cases’ as the reference group. Results: Of the respondents, 20.7% reported at least one LTC. The prevalence of CMDs increased with the number of LTCs, but over two-thirds (71.2%) of CMD cases in people with LTCs were untreated. Statistically significant PAFs were found for CMDs and recent hospital admission [13.5%, 95% confidence intervals (CI) 6.6–20.0] and severe disability (31.3%, 95% CI 27.1–35.2) after adjusting for LTCs and other confounders. Only the latter remained significant when using the most conservative estimate of PAF (21.8%, 95% CI 14.0–28.9), and this was reduced only slightly when considering only participants with LTCs (18.5%, 95% CI 7.9–27.9). Conclusions: Better treatments for CMDs in people with LTCs could achieve almost the same population health gain in terms of reducing severe disability as those targeted at the entire population. Interventions to reduce the prevalence of CMDs among people with LTCs should be part of routine medical care

Double photoionization of propylene oxide: a coincidence study of the ejection of a pair of valence-shell electrons

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms

Serum selenium concentrations and diabetes in U.S. adults : National Health and Nutrition Examination Survey (NHANES) 2003–2004

Background: Increasing evidence suggests that high selenium levels are associated with diabetes and other cardiometabolic risk factors. Objectives: We evaluated the association of serum selenium concentrations with fasting plasma glucose, glycosylated hemoglobin levels, and diabetes in the most recently available representative sample of the U.S. population. Methods: We used a cross-sectional analysis of 917 adults ≥ 40 years of age who had a fasting morning blood sample in the National Health and Nutrition Examination Survey 2003–2004. We evaluated the association of serum selenium, measured by inductively coupled plasma-dynamic reaction cell-mass spectrometry, and diabetes, defined as a self-report of current use of hypoglycemic agents or insulin or as fasting plasma glucose ≥ 126 mg/dL. Results: Mean serum selenium was 137.1 μg/L. The multivariable adjusted odds ratio [95% confidence interval (CI)] for diabetes comparing the highest quartile of serum selenium (≥ 147 μg/L) with the lowest (< 124 μg/L) was 7.64 (3.34–17.46). The corresponding average differences (95% CI) in fasting plasma glucose and glycosylated hemoglobin were 9.5 mg/dL (3.4–15.6 mg/dL) and 0.30% (0.14–0.46%), respectively. In spline regression models, the prevalence of diabetes as well as glucose and glycosylated hemoglobin levels increased with increasing selenium concentrations up to 160 μg/L. Conclusions: In U.S. adults, high serum selenium concentrations were associated with higher prevalence of diabetes and higher fasting plasma glucose and glycosylated hemoglobin levels. Given high selenium intake in the U.S. population, further research is needed to determine the role of excess selenium levels in the development or the progression of diabetes

Serum selenium levels do not differ in type 2 diabetic subjects with and without coronary artery disease

<p>Abstract</p> <p>Background</p> <p>The aim of the present study was to investigate whether selenium levels differ between type 2 diabetic subjects with and without coronary artery disease (CAD).</p> <p>Methods</p> <p>A total of 200 subjects with type 2 diabetes (100 with CAD and 100 without CAD), consecutively selected from the diabetes outpatient clinic of our hospital were enrolled into the study. A detailed medical history and a physical examination were obtained by all the participants.</p> <p>Results</p> <p>Serum selenium levels did not differ between diabetic subjects with and without CAD (102.40 ± 31.10 vs. 108.86 ± 33.88 microg/L, p = 0.16). In diabetic subjects with CAD multivariate linear regression analysis demonstrated significant independent associations between selenium and sex (beta = 0.21, p = 0.03) and glucose levels (beta = 0.25, p = 0.008). In diabetic subjects without CAD multivariate linear regression analysis demonstrated significant independent associations between selenium and peripheral artery disease (beta = 0.16, p = 0.05) and glucose levels (beta = -0.09, p = 0.05).</p> <p>Conclusion</p> <p>Serum selenium levels did not differ between diabetic subjects with and without CAD. In diabetic subjects with CAD, the only determinants of serum selenium levels were sex and glucose levels. In diabetic subjects without CAD the only determinants of serum selenium levels were peripheral artery disease and glucose levels.</p

Collective Autoionization in Multiply-Excited Systems: A novel ionization process observed in Helium Nanodroplets

Free electron lasers (FELs) offer the unprecedented capability to study reaction dynamics and image the structure of complex systems. When multiple photons are absorbed in complex systems, a plasma-like state is formed where many atoms are ionized on a femtosecond timescale. If multiphoton absorption is resonantly-enhanced, the system becomes electronically-excited prior to plasma formation, with subsequent decay paths which have been scarcely investigated to date. Here, we show using helium nanodroplets as an example that these systems can decay by a new type of process, named collective autoionization. In addition, we show that this process is surprisingly efficient, leading to ion abundances much greater than that of direct single-photon ionization. This novel collective ionization process is expected to be important in many other complex systems, e.g. macromolecules and nanoparticles, exposed to high intensity radiation fields

Real-time dynamics of the formation of hydrated electrons upon irradiation of water clusters with extreme ultraviolet light

Free electrons in a polar liquid can form a bound state via interaction with the molecular environment. This so-called hydrated electron state in water is of fundamental importance e.g.~in cellular biology or radiation chemistry. Hydrated electrons are highly reactive radicals that can either directly interact with DNA or enzymes, or form highly excited hydrogen (H∗) after being captured by protons. Here, we investigate the formation of the hydrated electron in real-time employing XUV femtosecond pulses from a free electron laser, in this way observing the initial steps of the hydration process. Using time-resolved photoelectron spectroscopy we find formation timescales in the low picosecond range and resolve the prominent dynamics of forming excited hydrogen states

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

Shift Work Is Not Associated with High Blood Pressure or Prevalence of Hypertension

Background: Working mostly at night has been suggested to be associated with upset of chronobiological rhythms and high blood pressure, but the evidence from epidemiological studies is weak. Methods: In a cross-sectional survey, we evaluated the association between shift work and blood pressure, pre-hypertension and hypertension. In total, 493 nurses, nurse technicians and assistants, were selected at random in a large general hospital setting. Hypertension was diagnosed by the mean of four automatic blood pressure readings $140/ 90 mmHg or use of blood pressure lowering agents, and pre-hypertension by systolic blood pressure$120–139 or diastolic blood pressure $80–89 mmHg. Risk factors for hypertension were evaluated by a standardized questionnaire and anthropometric measurements. The association between the shift of work and blood pressure, pre-hypertension and hypertension was explored using univariate and multivariate analyses that controlled for risk factors for hypertension by covariance analysis and modified Poisson regression. Results: The mean age of the participants was 34.369.4 years and 88.2 % were women. Night shift workers were older, more frequently married or divorced, and less educated. The prevalence of hypertension in the whole sample was 16%, and 28% had pre-hypertension. Blood pressure (after adjustment for confounding) was not different in day and night shift workers. The prevalence of hypertension and pre-hypertension by shift work was not different in the univariate analysis and afte