Vacuum-UV negative photoion spectroscopy of CH4

Using synchrotron radiation in the range 12-35 eV, negative ions are detected by mass spectrometry following vacuum-UV photoexcitation of methane. Ion yields for H$^-$, CH$^-$ and CH$_2^-$ are recorded, the spectra of CH$^-$ and CH$_2^-$ for the first time. All ions display a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation. Cross sections for ion-pair formation are put onto an absolute scale by calibrating the signal strengths with those of F$^-$ from SF$_6$ and CF$_4$. Following normalisation to total vacuum-UV absorption cross sections, quantum yields for anion production are reported. There is a major discrepancy in the H$^-$ cross section with an earlier measurement, which remains unresolved. The anions arise from both direct and indirect ion-pair mechanisms. For a generic polyatomic molecule AB, the former is defined as AB $\rightarrow$ A$^-$ + B$^+$ (+ neutrals), the latter as the predissociative crossing of an initially-excited Rydberg state of AB by an ion-pair state. In a separate experiment, the threshold photoelectron spectrum of the second valence band of CH$_4$, ionisation to CH$_4^+$ A $^2$A$_1$ at 22.4 eV, is recorded with an instrumental resolution of 0.004 eV; many of the Rydberg states observed in indirect ion-pair formation converge to this state. The widths of the peaks are lifetime limited, increasing with increasing $v$ in the $v_1$ (a$_1$) vibrational ladder. They are the first direct measurement of an upper value to the dissociation rate of these levels into fragment ions

Threshold photoelectron photoion coincidence spectroscopy of trichloroethene and tetrachloroethene

The threshold photoelectron, the threshold photoelectron photoion coincidence and ion breakdown spectra of trichloroethene and tetrachloroethene have been recorded from 9 – 22 eV. Comparisons with the equivalent data for the three dichloroethene molecules and theoretical calculations highlight the nature of the orbitals involved during photoionisation in this energy range. The ground electronic state of C$_2$HCl$_3^+$ (C$_2$Cl$_4^+$) is bound, with excited valence states dissociating to C$_2$HCl$_2^+$ (C$_2$Cl$_3^+$) and C$_2$HCl$^+$ (C$_2$Cl$_2^+$). Appearance energies suggest that C$_2$HCl$^+$ forms from C$_2$HCl$_3^+$ by loss of two chlorine atoms, whereas C$_2$Cl$_2^+$ forms from C$_2$Cl$_4^+$ by loss of a Cl$_2$ molecule. The translational kinetic energy release into C$_2$HCl$_2^+$ (C$_2$Cl$_3^+$) + Cl is determined as a function of energy. In both cases, the fraction of the available energy released into translational energy of the two products decreases as the photon energy increases

Mindfulness-based interventions in epilepsy: a systematic review

Mindfulness based interventions (MBIs) are increasingly used to help patients cope with physical and mental long-term conditions (LTCs). Epilepsy is associated with a range of mental and physical comorbidities that have a detrimental effect on quality of life (QOL), but it is not clear whether MBIs can help. We systematically reviewed the literature to determine the effectiveness of MBIs in people with epilepsy. Medline, Cochrane Central Register of Controlled Trials, EMBASE, CINAHL, Allied and Complimentary Medicine Database, and PsychInfo were searched in March 2016. These databases were searched using a combination of subject headings where available and keywords in the title and abstracts. We also searched the reference lists of related reviews. Study quality was assessed using the Cochrane Collaboration risk of bias tool. Three randomised controlled trials (RCTs) with a total of 231 participants were included. The interventions were tested in the USA (n = 171) and China (Hong Kong) (n = 60). Significant improvements were reported in depression symptoms, quality of life, anxiety, and depression knowledge and skills. Two of the included studies were assessed as being at unclear/high risk of bias - with randomisation and allocation procedures, as well as adverse events and reasons for drop-outs poorly reported. There was no reporting on intervention costs/benefits or how they affected health service utilisation. This systematic review found limited evidence for the effectiveness of MBIs in epilepsy, however preliminary evidence suggests it may lead to some improvement in anxiety, depression and quality of life. Further trials with larger sample sizes, active control groups and longer follow-ups are needed before the evidence for MBIs in epilepsy can be conclusively determined

Undecidable word problem in subshift automorphism groups

This article studies the complexity of the word problem in groups of automorphisms of subshifts. We show in particular that for any Turing degree, there exists a subshift whose automorphism group contains a subgroup whose word problem has exactly this degree

Population pharmacokinetics of intravenous artesunate: a pooled analysis of individual data from patients with severe malaria.

There are ~660,000 deaths from severe malaria each year. Intravenous artesunate (i.v. ARS) is the first-line treatment in adults and children. To optimize the dosing regimen of i.v. ARS, the largest pooled population pharmacokinetic study to date of the active metabolite dihydroartemisinin (DHA) was performed. The pooled dataset consisted of 71 adults and 195 children with severe malaria, with a mixture of sparse and rich sampling within the first 12 h after drug administration. A one-compartment model described the population pharmacokinetics of DHA adequately. Body weight had the greatest impact on DHA pharmacokinetics, resulting in lower DHA exposure for smaller children (6-10 kg) than adults. Post hoc estimates of DHA exposure were not significantly associated with parasitological outcomes. Comparable DHA exposure in smaller children and adults after i.v. ARS was achieved under a dose modification for intramuscular ARS proposed in a separate analysis of children

An algorithmic approach to the existence of ideal objects in commutative algebra

The existence of ideal objects, such as maximal ideals in nonzero rings, plays a crucial role in commutative algebra. These are typically justified using Zorn's lemma, and thus pose a challenge from a computational point of view. Giving a constructive meaning to ideal objects is a problem which dates back to Hilbert's program, and today is still a central theme in the area of dynamical algebra, which focuses on the elimination of ideal objects via syntactic methods. In this paper, we take an alternative approach based on Kreisel's no counterexample interpretation and sequential algorithms. We first give a computational interpretation to an abstract maximality principle in the countable setting via an intuitive, state based algorithm. We then carry out a concrete case study, in which we give an algorithmic account of the result that in any commutative ring, the intersection of all prime ideals is contained in its nilradical

Simpson's paradox visualized: The example of the Rosiglitazone meta-analysis

<p>Abstract</p> <p>Background</p> <p>Simpson's paradox is sometimes referred to in the areas of epidemiology and clinical research. It can also be found in meta-analysis of randomized clinical trials. However, though readers are able to recalculate examples from hypothetical as well as real data, they may have problems to easily figure where it emerges from.</p> <p>Method</p> <p>First, two kinds of plots are proposed to illustrate the phenomenon graphically, a scatter plot and a line graph. Subsequently, these can be overlaid, resulting in a overlay plot. The plots are applied to the recent large meta-analysis of adverse effects of rosiglitazone on myocardial infarction and to an example from the literature. A large set of meta-analyses is screened for further examples.</p> <p>Results</p> <p>As noted earlier by others, occurrence of Simpson's paradox in the meta-analytic setting, if present, is associated with imbalance of treatment arm size. This is well illustrated by the proposed plots. The rosiglitazone meta-analysis shows an effect reversion if all trials are pooled. In a sample of 157 meta-analyses, nine showed an effect reversion after pooling, though non-significant in all cases.</p> <p>Conclusion</p> <p>The plots give insight on how the imbalance of trial arm size works as a confounder, thus producing Simpson's paradox. Readers can see why meta-analytic methods must be used and what is wrong with simple pooling.</p

Reverse mathematics of matroids

Matroids generalize the familiar notion of linear dependence from linear algebra. Following a brief discussion of founding work in computability and matroids, we use the techniques of reverse mathematics to determine the logical strength of some basis theorems for matroids and enumerated matroids. Next, using Weihrauch reducibility, we relate the basis results to combinatorial choice principles and statements about vector spaces. Finally, we formalize some of the Weihrauch reductions to extract related reverse mathematics results. In particular, we show that the existence of bases for vector spaces of bounded dimension is equivalent to the induction scheme for \Sigma^0_2 formulas

A massive, quiescent galaxy at redshift of z=3.717

In the early Universe finding massive galaxies that have stopped forming stars present an observational challenge as their rest-frame ultraviolet emission is negligible and they can only be reliably identified by extremely deep near-infrared surveys. These have revealed the presence of massive, quiescent early-type galaxies appearing in the universe as early as z$\sim$2, an epoch 3 Gyr after the Big Bang. Their age and formation processes have now been explained by an improved generation of galaxy formation models where they form rapidly at z$\sim$3-4, consistent with the typical masses and ages derived from their observations. Deeper surveys have now reported evidence for populations of massive, quiescent galaxies at even higher redshifts and earlier times, however the evidence for their existence, and redshift, has relied entirely on coarsely sampled photometry. These early massive, quiescent galaxies are not predicted by the latest generation of theoretical models. Here, we report the spectroscopic confirmation of one of these galaxies at redshift z=3.717 with a stellar mass of 1.7$\times$10$^{11}$ M$_\odot$ whose absorption line spectrum shows no current star-formation and which has a derived age of nearly half the age of the Universe at this redshift. The observations demonstrates that the galaxy must have quickly formed the majority of its stars within the first billion years of cosmic history in an extreme and short starburst. This ancestral event is similar to those starting to be found by sub-mm wavelength surveys pointing to a possible connection between these two populations. Early formation of such massive systems is likely to require significant revisions to our picture of early galaxy assembly.Comment: 6 pages, 7 figures. This is the final preprint corresponding closely to the published version. Uploaded 6 months after publication in accordance with Nature polic

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