Molecular double core-hole electron spectroscopy for chemical analysis

We explore the potential of double core hole electron spectroscopy for chemical analysis in terms of x-ray two-photon photoelectron spectroscopy (XTPPS). The creation of deep single and double core vacancies induces significant reorganization of valence electrons. The corresponding relaxation energies and the interatomic relaxation energies are evaluated by CASSCF calculations. We propose a method how to experimentally extract these quantities by the measurement of single and double core-hole ionization potentials (IPs and DIPs). The influence of the chemical environment on these DIPs is also discussed for states with two holes at the same atomic site and states with two holes at two different atomic sites. Electron density difference between the ground and double core-hole states clearly shows the relaxations accompanying the double core-hole ionization. The effect is also compared with the sensitivity of single core hole ionization potentials (IPs) arising in single core hole electron spectroscopy. We have demonstrated the method for a representative set of small molecules LiF, BeO, BF, CO, N2, C2H2, C2H4, C2H6, CO2 and N2O. The scalar relativistic effect on IPs and on DIPs are briefly addressed.Comment: 35 pages, 6 figures. To appear in J. Chem. Phys

Enabling energy system transition toward decarbonization in Japan through energy service demand reduction

Japan's mid-century strategy for reducing greenhouse gas emissions by 80% in 2050 would require large-scale energy system transformation and associated increases in mitigation costs. Nevertheless, the role of energy demand reduction, especially reductions related to energy services such as behavioral changes and material use efficiency improvements, have not been sufficiently evaluated. This study aims to identify key challenges and opportunities of the decarbonization goal when considering the role of energy service demand reduction. To this end, we used a detailed bottom-up energy system model in conjunction with an energy service demand model to explore energy system changes and their cost implications. The results indicate that final energy demand in 2050 can be cut by 37% relative to the no-policy case through energy service demand reduction measures. Although the lack of carbon capture and storage would cause mitigation costs to double or more, these economic impacts can be offset by energy service demand reduction. Among energy demand sectors, the impact of industrial service demand reduction is largest, as it contributes to reducing residual emissions from the industry sector. These findings highlight the importance of energy service demand reduction measures for meeting national climate goals in addition to technological options

Association between exposure to environmental tobacco smoke and biomarkers of oxidative stress among patients hospitalised with acute myocardial infarction

Objective To determine whether exposure to environmental tobacco smoke was associated with oxidative stress among patients hospitalised for acute myocardial infarction.<p></p> Design An existing cohort study of 1,261 patients hospitalised for acute myocardial infarction.<p></p> Setting Nine acute hospitals in Scotland.<p></p> Participants Sixty never smokers who had been exposed to environmental tobacco smoke (admission serum cotinine ≥3.0 ng/mL) were compared with 60 never smokers who had not (admission serum cotinine ≤0.1 ng/mL).<p></p> Intervention None.<p></p> Main outcome measures Three biomarkers of oxidative stress (protein carbonyl, malondialdehyde (MDA) and oxidised low-density lipoprotein (ox-LDL)) were measured on admission blood samples and adjusted for potential confounders.<p></p> Results After adjusting for baseline differences in age, sex and socioeconomic status, exposure to environmental tobacco smoke was associated with serum concentrations of both protein carbonyl (beta coefficient 7.96, 95% CI 0.76, 15.17, p = 0.031) and MDA (beta coefficient 10.57, 95% CI 4.32, 16.81, p = 0.001) but not ox-LDL (beta coefficient 2.14, 95% CI −8.94, 13.21, p = 0.703).<p></p> Conclusions Exposure to environmental tobacco smoke was associated with increased oxidative stress. Further studies are requires to explore the role of oxidative stress in the association between environmental tobacco smoke and myocardial infarction.<p></p&gt

The Mechanisms of Codon Reassignments in Mitochondrial Genetic Codes

Many cases of non-standard genetic codes are known in mitochondrial genomes. We carry out analysis of phylogeny and codon usage of organisms for which the complete mitochondrial genome is available, and we determine the most likely mechanism for codon reassignment in each case. Reassignment events can be classified according to the gain-loss framework. The gain represents the appearance of a new tRNA for the reassigned codon or the change of an existing tRNA such that it gains the ability to pair with the codon. The loss represents the deletion of a tRNA or the change in a tRNA so that it no longer translates the codon. One possible mechanism is Codon Disappearance, where the codon disappears from the genome prior to the gain and loss events. In the alternative mechanisms the codon does not disappear. In the Unassigned Codon mechanism, the loss occurs first, whereas in the Ambiguous Intermediate mechanism, the gain occurs first. Codon usage analysis gives clear evidence of cases where the codon disappeared at the point of the reassignment and also cases where it did not disappear. Codon disappearance is the probable explanation for stop to sense reassignments and a small number of reassignments of sense codons. However, the majority of sense to sense reassignments cannot be explained by codon disappearance. In the latter cases, by analysis of the presence or absence of tRNAs in the genome and of the changes in tRNA sequences, it is sometimes possible to distinguish between the Unassigned Codon and Ambiguous Intermediate mechanisms. We emphasize that not all reassignments follow the same scenario and that it is necessary to consider the details of each case carefully.Comment: 53 pages (45 pages, including 4 figures + 8 pages of supplementary information). To appear in J.Mol.Evo

Right coronary wall cmr in the older asymptomatic advance cohort: positive remodeling and associations with type 2 diabetes and coronary calcium

<p>Abstract</p> <p>Background</p> <p>Coronary wall cardiovascular magnetic resonance (CMR) is a promising noninvasive approach to assess subclinical atherosclerosis, but data are limited in subjects over 60 years old, who are at increased risk. The purpose of the study was to evaluate coronary wall CMR in an asymptomatic older cohort.</p> <p>Results</p> <p>Cross-sectional images of the proximal right coronary artery (RCA) were acquired using spiral black-blood coronary CMR (0.7 mm resolution) in 223 older, community-based patients without a history of cardiovascular disease (age 60-72 years old, 38% female). Coronary measurements (total vessel area, lumen area, wall area, and wall thickness) had small intra- and inter-observer variabilities (r = 0.93~0.99, all p < 0.0001), though one-third of these older subjects had suboptimal image quality. Increased coronary wall thickness correlated with increased coronary vessel area (p < 0.0001), consistent with positive remodeling. On multivariate analysis, type 2 diabetes was the only risk factor associated with increased coronary wall area and thickness (p = 0.03 and p = 0.007, respectively). Coronary wall CMR measures were also associated with coronary calcification (p = 0.01-0.03).</p> <p>Conclusions</p> <p>Right coronary wall CMR in asymptomatic older subjects showed increased coronary atherosclerosis in subjects with type 2 diabetes as well as coronary calcification. Coronary wall CMR may contribute to the noninvasive assessment of subclinical coronary atherosclerosis in older, at-risk patient groups.</p

Frequentist Coverage Properties of Uncertainty Intervals for Weak Poisson Signals in the Presence of Background

We construct uncertainty intervals for weak Poisson signals in the presence of background. We consider the case where a primary experiment yields a realization of the signal plus background, and a second experiment yields a realization of the background. The data acquisitions times for the background-only experiment,T_bg, and the primary experiment,T, are selected so that their ratio varies from 1 to 25. The expected number of background counts in the primary experiment varies from 0.2 to 2. We construct 90 and 95 percent confidence intervals based on a propagation-of-errors method as well as two implementations of a Neyman procedure where acceptance regions are constructed based on a likelihood-ratio criterion that automatically determines whether the resulting confidence interval is one-sided or two-sided. The first Neyman procedure (due to Feldman and Cousins) neglects uncertainty in the background. In the other Neyman procedure, we account for uncertainty in the background with a parametric bootstrap method. We also construct minimum length Bayesian credibility intervals. For each method, we test for the presence of a signal based on the value of the lower endpoint of the uncertainty interval. When T_bg/T is 5 or more and the expected background is 2 or less, the Feldman Cousins method outperforms the other methods considered.Comment: 12 pages,12 tables, 10 figures. This is the final version of a manuscript that has been accepted for publication by Measurement Science and Technolog