The formation, dissociation and reactivity of gaseous ions

This thesis presents the results of a series of experiential investigations into the formation, dissociation and reactivity of gaseous ions. Firstly, using a time-of-flight mass spectrometer coupled with a 2D ion coincidence technique, studies of the electron ionization of a number of small gas-phase molecules are presented. Relative partial ionization cross-sections (PICS) are derived for the formation of positively charged fragment ions, following electron ionization of H2S, CH3OH and CF3I. The 2D ion coincidence technique enables fragment ions formed by dissociative single, double, triple and quadruple ionization to be distinguished and quantified. This information also allows precursor specific relative PICS to be determined. While the relative PICS quantify the overall yield of each fragment ion, the precursor specific relative PICS quantify the contribution from single, double, triple and quadruple ionization to the relative yields of each fragment ion. Such information is essential for the accurate modelling, and the understanding, of the chemical processes occurring in energetic environments, such as industrial plasmas and planetary atmospheres. Comparison of the relative PICS data to existing measurements of the PICS for these molecules generally shows good agreement for experiments in which the efficient collection of translationally energetic ions is demonstrated. In addition, information on the energetics and dissociation dynamics involved in the fragmentation of H2S2+, CH3OH2+, CF3I2+ and CF3I3+ are provided by interpretation of ion pair peaks recorded in the 2D ion coincidence spectra. Secondly, this thesis also presents the results of an investigation into the photoionization of CF3I, using the threshold photoelectron-photoion-photoion coincidence (iPEPICO) endstation on the vacuum-ultraviolet beamline at the Swiss Light Source. These experiments were part of a scoping study to see if this existing apparatus could be used to study multiple ionization. The photoionization spectra are interpreted and discussed, and issues with the current experimental arrangement, which may be improved for future visits, are addressed. Finally, studies of I2+ collisions with OCS, carried out using a crossed ion beam experiment with a time-of-flight mass spectrometer, are presented. Two bond-forming reactions producing IO+ and IS+ are observed, together with the more ubiquitous electron transfer reactions. These electron transfer reactions are rationalised using the Reaction Window model

Interannual variability of tropical cyclone activity along the Pacific coast of North America

AbstractThe interannual variability of near-coastal eastern North Pacific tropical cyclones is described using a data set of cyclone tracks constructed from U.S. and Mexican oceanic and atmospheric reports for the period 1951-2006. Near-coastal cyclone counts are enumerated monthly, allowing us to distinguish interannual variability during different phases of the May-November tropical cyclone season. In these data more tropical cyclones affect the Pacific coast in May-July, the early months of the tropical cyclone season, during La Niña years, when equatorial Pacific sea surface temperatures are anomalously cool, than during El Niño years. The difference in early season cyclone counts between La Niña and El Niño years was particularly pronounced during the mid-twentieth century epoch when cool equatorial temperatures were enhanced as described by an index of the Pacific Decadal Oscillation. Composite maps from years with high and low near-coastal cyclone counts show that the atmospheric circulation anomalies associated with cool sea surface temperatures in the eastern equatorial Pacific are consistent with preferential steering of tropical cyclones northeastward toward the west coast of Mexico

Symmetric Dimethylarginine Is Not Associated with Cumulative Inflammatory Load or Classical Cardiovascular Risk Factors in Rheumatoid Arthritis: A 6-Year Follow-Up Study

Symmetric dimethylarginine (SDMA) indirectly inhibits nitric oxide (NO) synthesis and predicts cardiovascular and all-cause mortality in high-risk patients. The aim of our study was to investigate the associations of cumulative inflammatory burden (assessed by serial measurements of inflammatory markers) and classical cardiovascular (CV) disease risk factors with SDMA in RA patients. 201 RA patients (155 females, median age 67 (59�73)) were assessed at baseline (2006). Classical CV disease risk factors were recorded and systemic inflammation was determined by themeasurement of C-reactive protein (CRP) and erythrocyte sedimentation rate (ESR). At follow-up (2012) SDMA levels were measured by enzyme-linked immunosorbent assay.Mean SDMA levels in RA population were 0.40 (0.40�0.53) ����mol/L. No significant association between SDMA and cumulative inflammatory load was established in the analysis. SDMA levels were not found to be significantly related to CV disease risk factors.We explored the potential relationship between SDMA and cumulative inflammatory burden in patients with RA and obtained negative results. SDMA did not relate to CV disease risk factors in our population and its clinical significance as a surrogate marker of endothelial dysfunction in patients with RA remains to be determined

Induced CMB quadrupole from pointing offsets

Recent claims in the literature have suggested that the {\it WMAP} quadrupole is not primordial in origin, and arises from an aliasing of the much larger dipole field because of incorrect satellite pointing. We attempt to reproduce this result and delineate the key physics leading to the effect. We find that, even if real, the induced quadrupole would be smaller than claimed. We discuss reasons why the {\it WMAP} data are unlikely to suffer from this particular systematic effect, including the implications for observations of point sources. Given this evidence against the reality of the effect, the similarity between the pointing-offset-induced signal and the actual quadrupole then appears to be quite puzzling. However, we find that the effect arises from a convolution between the gradient of the dipole field and anisotropic coverage of the scan direction at each pixel. There is something of a directional conspiracy here -- the dipole signal lies close to the Ecliptic Plane, and its direction, together with the {\it WMAP} scan strategy, results in a strong coupling to the $Y_{2,\,-1}$ component in Ecliptic co-ordinates. The dominant strength of this component in the measured quadrupole suggests that one should exercise increased caution in interpreting its estimated amplitude. The {\it Planck} satellite has a different scan strategy which does not so directly couple the dipole and quadrupole in this way and will soon provide an independent measurement.Comment: 8 pages, 4 figure

Embryonic expression and cloning of the murine GATA-3 gene.

We describe the embryonic expression pattern as well as the cloning and initial transcriptional regulatory analysis of the murine (m) GATA-3 gene. In situ hybridization shows that mGATA-3 mRNA accumulation is temporally and spatially regulated during early development: although found most abundantly in the placenta prior to 10 days of embryogenesis, mGATA-3 expression becomes restricted to specific cells within the embryonic central nervous system (in the mesencephalon, diencephalon, pons and inner ear) later in gestation. GATA-3 also shows a restricted expression pattern in the peripheral nervous system, including terminally differentiating cells in the cranial and sympathetic ganglia. In addition to this distinct pattern in the nervous system, mGATA-3 is also expressed in the embryonic kidney and the thymic rudiment, and further analysis showed that it is expressed throughout T lymphocyte differentiation. To begin to investigate how this complex gene expression pattern is elicited, cloning and transcriptional regulatory analyses of the mGATA-3 gene were initiated. At least two regulatory elements (one positive and one negative) appear to be required for appropriate tissue-restricted regulation after transfection of mGATA-3-directed reporter genes into cells that naturally express GATA-3 (T lymphocytes and neuroblastoma cells). Furthermore, this same region of the locus confers developmentally appropriate expression in transgenic mice, but only in a subset of the tissues that naturally express the gene

Surface Instability in Windblown Sand

We investigate the formation of ripples on the surface of windblown sand based on the one-dimensional model of Nishimori and Ouchi [Phys. Rev. Lett. 71, 197 (1993)], which contains the processes of saltation and grain relaxation. We carry out a nonlinear analysis to determine the propagation speed of the restabilized ripple patterns, and the amplitudes and phases of their first, second, and third harmonics. The agreement between the theory and our numerical simulations is excellent near the onset of instability. We also determine the Eckhaus boundary, outside which the steady ripple patterns are unstable.Comment: 23 pages, 8 figure

Experimental and Theoretical Investigation of the Reaction of NH2 with NO at Very Low Temperatures

The first experimental study of the low-temperature kinetics of the gas-phase reaction between NH2 and NO has been performed. A pulsed laser photolysis-laser-induced fluorescence technique was used to create and monitor the temporal decay of NH2 in the presence of NO. Measurements were carried out over the temperature range of 24–106 K, with the low temperatures achieved using a pulsed Laval nozzle expansion. The negative temperature dependence of the reaction rate coefficient observed at higher temperatures in the literature continues at these lower temperatures, with the rate coefficient reaching 3.5 × 10–10 cm3 molecule–1 s–1 at T = 26 K. Ab initio calculations of the potential energy surface were combined with rate theory calculations using the MESMER software package in order to calculate and predict rate coefficients and branching ratios over a wide range of temperatures, which are largely consistent with experimentally determined literature values. These theoretical calculations indicate that at the low temperatures investigated for this reaction, only one product channel producing N2 + H2O is important. The rate coefficients determined in this study were used in a gas-phase astrochemical model. Models were run over a range of physical conditions appropriate for cold to warm molecular clouds (10 to 30 K; 104 to 106 cm–3), resulting in only minor changes (<1%) to the abundances of NH2 and NO at steady state. Hence, despite the observed increase in the rate at low temperatures, this mechanism is not a dominant loss mechanism for either NH2 or NO under dark cloud conditions

No evidence for anomalously low variance circles on the sky

In a recent paper, Gurzadyan & Penrose claim to have found directions on the sky centred on which are circles of anomalously low variance in the cosmic microwave background (CMB). These features are presented as evidence for a particular picture of the very early Universe. We attempted to repeat the analysis of these authors, and we can indeed confirm that such variations do exist in the temperature variance for annuli around points in the data. However, we find that this variation is entirely expected in a sky which contains the usual CMB anisotropies. In other words, properly simulated Gaussian CMB data contain just the sorts of variations claimed. Gurzadyan & Penrose have not found evidence for pre-Big Bang phenomena, but have simply re-discovered that the CMB contains structure.Comment: 4 pages, 4 figures, v3 accepted by JCA

Dimensionless cosmology

Although it is well known that any consideration of the variations of fundamental constants should be restricted to their dimensionless combinations, the literature on variations of the gravitational constant $G$ is entirely dimensionful. To illustrate applications of this to cosmology, we explicitly give a dimensionless version of the parameters of the standard cosmological model, and describe the physics of Big Bang Neucleosynthesis and recombination in a dimensionless manner. The issue that appears to have been missed in many studies is that in cosmology the strength of gravity is bound up in the cosmological equations, and the epoch at which we live is a crucial part of the model. We argue that it is useful to consider the hypothetical situation of communicating with another civilization (with entirely different units), comparing only dimensionless constants, in order to decide if we live in a Universe governed by precisely the same physical laws. In this thought experiment, we would also have to compare epochs, which can be defined by giving the value of any {\it one} of the evolving cosmological parameters. By setting things up carefully in this way one can avoid inconsistent results when considering variable constants, caused by effectively fixing more than one parameter today. We show examples of this effect by considering microwave background anisotropies, being careful to maintain dimensionlessness throughout. We present Fisher matrix calculations to estimate how well the fine structure constants for electromagnetism and gravity can be determined with future microwave background experiments. We highlight how one can be misled by simply adding $G$ to the usual cosmological parameter set