Two-Dimensional Partial-Covariance Mass Spectrometry of Large Molecules Based on Fragment Correlations

Covariance mapping [L. J. Frasinski, K. Codling, and P. A. Hatherly, Science 246, 1029 (1989)] is a well-established technique used for the study of mechanisms of laser-induced molecular ionization and decomposition. It measures statistical correlations between fluctuating signals of pairs of detected species (ions, fragments, electrons). A positive correlation identifies pairs of products originating from the same dissociation or ionization event. A major challenge for covariance-mapping spectroscopy is accessing decompositions of large polyatomic molecules, where true physical correlations are overwhelmed by spurious signals of no physical significance induced by fluctuations in experimental parameters. As a result, successful applications of covariance mapping have so far been restricted to low-mass systems, e.g., organic molecules of around 50 daltons (Da). Partial-covariance mapping was suggested to tackle the problem of spurious correlations by taking into account the independently measured fluctuations in the experimental conditions. However, its potential has never been realized for the decomposition of large molecules, because in these complex situations, determining and continuously monitoring multiple experimental parameters affecting all the measured signals simultaneously becomes unfeasible. We introduce, through deriving theoretically and confirming experimentally, a conceptually new type of partial-covariance mapping—self-correcting partial-covariance spectroscopy—based on a parameter extracted from the measured spectrum itself. We use the readily available total ion count as the self-correcting partial-covariance parameter, thus eliminating the challenge of determining experimental parameter fluctuations in covariance measurements of large complex systems. The introduced self-correcting partial covariance enables us to successfully resolve correlations of molecules as large as 10 3 – 10 4     Da , 2 orders of magnitude above the state of the art. This opens new opportunities for mechanistic studies of large molecule decompositions through revealing their fragment-fragment correlations. Moreover, we demonstrate that self-correcting partial covariance is applicable to solving the inverse problem: reconstruction of a molecular structure from its fragment spectrum, within two-dimensional partial-covariance mass spectrometry

Geologic Evaluation of Critical Production Parameters for Coalbed Methane Resources: Part 1, San Juan Basin

The Fruitland Formation in the San Juan Basin is the major producer of coalbed methane in the Western U.S. Forty-three to forty-nine Tcf of methane occur in 245 billion short tons of Fruitland coal at depths between 400 and 4,200 ft. Thickest Fruitland coal seams trend northwest and occur in the northern part of the basin, northeast of a syndepositional, structural hinge line; they occur in coastal plain facies southwest of Pictured Cliffs barrier/strandplain sandstones. South of the hinge line, northeast-trending coal seams occur in floodplain facies between northeast-trending Fruitland fluvial systems. Face cleat trends in Fruitland coal seams are predominantly northeast in the southern two-thirds of the basin and northwest but variable in the northern third. Suggested targets for enhanced coalbed permeability are tectonic fractures and fractures associated with subtle folds. Fruitland Formation waters are evolved meteoric waters; water composition reflects hydrologic setting. Waters in the north-central San Juan Basin have high alkalinity and low chlorinity; waters in the southern part are Na-Cl type. Distribution of low-chloride ground water in the Fruitland Formation in the north-central basin coincides with the overpressured area and with flow patterns inferred from the head map. The Fruitland Formation acts regionally as a single hydrologic unit or homogeneous aquifer, but large pressure gradients locally indicate that Fruitland strata may be hydraulically disconnected and behave at the field scale as compartmentalized aquifers. Hydrologic studies defined reservoir characteristics and permeability boundaries in the Fruitland Formation. Geologic and hydrologic parameters were used to divide the San Juan Basin into areas in which coal beds have similar reservoir characteristics. Coalbed wells have negative declines early in their production history followed by exponential decline rates at less than 5 percent/year. Sandstone wells that exhibit coal-decline behavior probably are producing coalbed methane indirectly from coal seams.Bureau of Economic Geolog

Health economic evaluations of preventative care for perinatal anxiety and associated disorders: a rapid review

Objectives Perinatal mental health problems affect one in five women and cost the UK £8.1 billion for every year of births, with 72% of this cost due to the long-term impact on the child. We conducted a rapid review of health economic evaluations of preventative care for perinatal anxiety and associated disorders. Design This study adopted a rapid review approach, using principles of the standard systematic review process to generate quality evidence. This methodology features a systematic database search, Preferred Reporting Items for Systematic Reviews and Meta-Analyses diagram, screening of evidence, data extraction, critical appraisal and narrative synthesis. Data sources PubMed, Cumulative Index to Nursing and Allied Health Literature, Cochrane Library, Applied Social Sciences Index and Abstracts, PsycINFO and MEDLINE. Eligibility criteria for selecting studies Studies that evaluated the costs and cost-effectiveness of preventative care for perinatal anxiety and associated disorders carried out within the National Health Service and similar healthcare systems. Data extraction and synthesis A minimum of two independent reviewers used standardised methods to search, screen, critically appraise and synthesise included studies. Results The results indicate a lack of economic evaluation specifically for perinatal anxiety, with most studies focusing on postnatal depression (PND). Interventions to prevent postnatal mental health problems are cost-effective. Modelling studies have also been conducted, which suggest that treating PND with counselling would be cost-effective. Conclusion The costs of not intervening in maternal mental health outweigh the costs of preventative interventions. Preventative measures such as screening and counselling for maternal mental health are shown to be cost-effective interventions to improve outcomes for women and children

Virial theorem in the Kohn-Sham density-functional theory formalism: Accurate calculation of the atomic quantum theory of atoms in molecules energies

A new approach for computing the atom-in-molecule [quantum theory of atoms in molecule (QTAIM)] energies in Kohn-Sham density-functional theory is presented and tested by computing QTAIM energies for a set of representative molecules. In the new approach, the contribution for the correlation-kinetic energy (

The Physicist's Guide to the Orchestra

An experimental study of strings, woodwinds (organ pipe, flute, clarinet, saxophone and recorder), and the voice was undertaken to illustrate the basic principles of sound production in music instruments. The setup used is simple and consists of common laboratory equipment. Although the canonical examples (standing wave on a string, in an open and closed pipe) are easily reproduced, they fail to explain the majority of the measurements. The reasons for these deviations are outlined and discussed.Comment: 11 pages, 10 figures (jpg files). Submitted to European Journal of Physic

Modeling Supply Networks and Business Cycles as Unstable Transport Phenomena

Physical concepts developed to describe instabilities in traffic flows can be generalized in a way that allows one to understand the well-known instability of supply chains (the so-called ``bullwhip effect''). That is, small variations in the consumption rate can cause large variations in the production rate of companies generating the requested product. Interestingly, the resulting oscillations have characteristic frequencies which are considerably lower than the variations in the consumption rate. This suggests that instabilities of supply chains may be the reason for the existence of business cycles. At the same time, we establish some link to queuing theory and between micro- and macroeconomics.Comment: For related work see http://www.helbing.or

Response function analysis of excited-state kinetic energy functional constructed by splitting k-space

Over the past decade, fundamentals of time independent density functional theory for excited state have been established. However, construction of the corresponding energy functionals for excited states remains a challenging problem. We have developed a method for constructing functionals for excited states by splitting k-space according to the occupation of orbitals. In this paper we first show the accuracy of kinetic energy functional thus obtained. We then perform a response function analysis of the kinetic energy functional proposed by us and show why method of splitting the k-space could be the method of choice for construction of energy functionals for excited states.Comment: 11 page

Silicon carbide particulates incorporated into microalloyed steel surface using TIG: microstructure and properties

Surface metal matrix composites have been developed to enhance properties such as erosion, wear and corrosion of alloys. In this study, ~5 µm or ~75 µm SiC particulates were preplaced on a microalloyed steel. Single track surface zones were melted by a tungsten inert gas torch, and the effect of two heat inputs, 420Jmm-1 and 840 Jmm-1,compared. The results showed that the samples melted using 420Jmm-1 were crack-free. Pin-on-disk wear testing under dry sliding conditions were conducted. The effects of load and sliding velocity were used to characterise the performance of the crack-free samples. Microstructural and X-ray diffraction studies of the surface showed that the SiC had dissolved, and that martensite, was the main phase influencing the hardness

The promise of microarrays in the management and treatment of breast cancer

Breast cancer is the most common malignancy afflicting women from Western cultures. Developments in breast cancer molecular and cellular biology research have brought us closer to understanding the genetic basis of this disease. Recent advances in microarray technology hold the promise of further increasing our understanding of the complexity and heterogeneity of this disease, and providing new avenues for the prognostication and prediction of breast cancer outcomes. These new technologies have some limitations and have yet to be incorporated into clinical use, for both the diagnosis and treatment of women with breast cancer. The most recent application of microarray genomic technologies to studying breast cancer is the focus of this review