Spectroscopy and interactions of metal and metal cation complexes

The work in this thesis looks at the spectroscopy and interactions of metals and metal cation complexes. There are two aspects of this vast subject that are considered: the electronic spectroscopy of Au-RG complexes and the ion-molecule chemistry of metals important in the mesosphere-lower thermosphere (MLT) region of the atmosphere. The spectroscopy of the molecular states in the vicinity of the strong Au 2P3/2, 1/2 ← 2S1/2 atomic transition, have been studied for the Au-RG (RG = Ne, Ar, Kr, Xe) series using resonance enhanced multiphoton ionization (REMPI). The spectroscopy of these systems was more involved than expected and high level ab initio calculations were required to complement and aid interpretation of the REMPI spectra obtained. Two main effects were seen to influence the spectroscopy in this energetic region — the mixing between D2Π1/2 and E2Σ1/2+ states through spin-orbit interactions and the interaction of lower lying states arising from the Au(2D) + RG (1S0) asymptote, resulting in predissociation being observed. The MLT is the only region of the Earth’s atmosphere in which metals exist in a free atomic state. It is known that their presence in this region occurs via the ablation of meteors entering the upper atmosphere, but certain aspects of their chemistry are still unclear. Using high level ab initio theory, spectroscopic constants were determined for metal cation complexes that can be formed in this region. These values are used by collaborators in conjunction with laboratory measurement to establish accurate rate coefficients that will allow the ion-molecule chemistry of calcium and magnesium in the MLT region to be modelled

Spectroscopy and interactions of metal and metal cation complexes

The work in this thesis looks at the spectroscopy and interactions of metals and metal cation complexes. There are two aspects of this vast subject that are considered: the electronic spectroscopy of Au-RG complexes and the ion-molecule chemistry of metals important in the mesosphere-lower thermosphere (MLT) region of the atmosphere. The spectroscopy of the molecular states in the vicinity of the strong Au 2P3/2, 1/2 ← 2S1/2 atomic transition, have been studied for the Au-RG (RG = Ne, Ar, Kr, Xe) series using resonance enhanced multiphoton ionization (REMPI). The spectroscopy of these systems was more involved than expected and high level ab initio calculations were required to complement and aid interpretation of the REMPI spectra obtained. Two main effects were seen to influence the spectroscopy in this energetic region — the mixing between D2Π1/2 and E2Σ1/2+ states through spin-orbit interactions and the interaction of lower lying states arising from the Au(2D) + RG (1S0) asymptote, resulting in predissociation being observed. The MLT is the only region of the Earth’s atmosphere in which metals exist in a free atomic state. It is known that their presence in this region occurs via the ablation of meteors entering the upper atmosphere, but certain aspects of their chemistry are still unclear. Using high level ab initio theory, spectroscopic constants were determined for metal cation complexes that can be formed in this region. These values are used by collaborators in conjunction with laboratory measurement to establish accurate rate coefficients that will allow the ion-molecule chemistry of calcium and magnesium in the MLT region to be modelled

How Messages about COVID-19 May Have Affected People’s Sense of Threat and Mental Health

COVID-19 has had profound effects on many physical, mental and social aspects of health. This study examined people’s fears and concerns about the virus, their experiences of being subjected to expert opinion and media portrayals of suffering from the virus, experiences of lockdown, and hopes and doubts for the future. We also examined how these relate to symptoms of depression, anxiety and stress. 180 participants completed an online survey exploring the themes of the study. Results suggest that in addition to concerns of catching the virus themselves, participants were more concerned with passing it on to others. People found information provided by experts at times contradictory and confusing. There was a strong endorsement that the media exploited suffering and while there was a high desire to move to a more compassionate ‘caring and sharing world’, there were strong doubts that this would happen or that politicians would be able to navigate to that. More research is needed on how to present information about high levels of threat, tragic events and processes in order to avoid adding to, rather than reducing mental health difficulties, and generating unhelpful behaviours

Search for Scutellonema bradys resistance in yams (Dioscorea spp.)

A study to examine variability in susceptibility of yams to Scutellonema bradys and to identify possible sources of resistance in Ghanaian yam germplasm (Dioscorea spp.) for use in yam improvement programmes, particularly, in West Africa was undertaken. Pot and field screening methodologies were used. In general, S. bradys and dry rot of tuber symptoms as well as tuber cracking increased during the storage period. The study showed a positive correlation between visual nematode damage and population densities in yam tubers. There was also a linear relationship between dry rot disease and tuber cracking at harvest and during storage. This confirms that S. bradys causes dry rot of tubers resulting in external cracking of yam tubers. Positive linear relationship was also observed between yam tuber weight loss and dry rot disease indicating that dry rot disease may have contributed to the tuber weight loss. Therefore, tuber dry rot symptoms caused by S. bradys of yams could be used to discard susceptible yams at harvest and after a period of storage. However, there was no linear relationship between nematode population densities in yam tubers and roots, therefore, a root protocol cannot be used for assessing resistance in yams as it could lead to misclassification. The yam germplasm screened, reaffirmed resistance to S. bradys in Dioscorea dumetorum var. Nkanfo and D. cayenensis var. Afun

Anthropogenic resource subsidies and host-parasite dynamics in wildlife

Peer reviewe

Μελέτη επιπτώσεων συνδρομολόγησηςεφαρμογών σε πολυπύρηνες αρχιτεκτονικές

Understanding viral transmission dynamics within populations of reservoir hosts can facilitate greater knowledge of the spillover of emerging infectious diseases. While bat-borne viruses are of concern to public health, investigations into their dynamics have been limited by a lack of longitudinal data from individual bats. Here, we examine capture-mark-recapture (CMR) data from a species of Australian bat (Myotis macropus) infected with a putative novel Alphacoronavirus within a Bayesian framework. Then, we developed epidemic models to estimate the effect of persistently infectious individuals (which shed viruses for extensive periods) on the probability of viral maintenance within the study population. We found that the CMR data analysis supported grouping of infectious bats into persistently and transiently infectious bats. Maintenance of coronavirus within the study population was more likely in an epidemic model that included both persistently and transiently infectious bats, compared with the epidemic model with non-grouping of bats. These findings, using rare CMR data from longitudinal samples of individual bats, increase our understanding of transmission dynamics of bat viral infectious diseases

Contact Networks and Mortality Patterns Suggest Pneumonia-Causing Pathogens may Persist in Wild Bighorn Sheep

Efficacy of disease control efforts is often contingent on whether the disease persists locally in the host population or is repeatedly introduced from an alternative host species. Local persistence is partially determined by the interaction between host contact structure and disease transmission rates: relatively isolated host groups facilitate pathogen persistence by slowing the rate at which highly transmissible pathogens access new susceptibles; alternatively, isolated host groups impede persistence for pathogens with low transmission rates by limiting the number of available hosts and forcing premature fade-out. Here, we use long-term data from the Hells Canyon region to investigate whether variable host contact patterns are associated with survival outcomes for 46 cohorts of bighorn sheep (Ovis canadensis) lambs subject to recurrent pneumonia outbreaks. We build social contact networks for each lamb cohort, and quantify variation in lamb mortality attributable to populations, years, and groups. We then refine estimates of chronic carriage rates in ewes, and disease-induced mortality rates in lambs, by finding parameters for the disease process that produce lamb morality rates similar to those observed when simulated on the observed host contact networks. Our results suggest that summer lamb hazards are spatially structured at the subpopulation level: 92.5 percent of the variation in lamb hazards during pneumonia outbreak years was attributable to sub-population-level groups, whereas 1.7 percent and 5.6 percent were attributable to year and population, respectively.  Additionally, the posterior distribution generated by our disease transmission model suggests that pneumonia-causing pathogens may persist locally in bighorn sheep populations, even during apparently healthy years

The problem of scale in the prediction and management of pathogen spillover

Disease emergence events, epidemics and pandemics all underscore the need to predict zoonotic pathogen spillover. Because cross-species transmission is inherently hierarchical, involving processes that occur at varying levels of biological organization, such predictive efforts can be complicated by the many scales and vastness of data potentially required for forecasting. A wide range of approaches are currently used to forecast spillover risk (e.g. macroecology, pathogen discovery, surveillance of human populations, among others), each of which is bound within particular phylogenetic, spatial and temporal scales of prediction. Here, we contextualize these diverse approaches within their forecasting goals and resulting scales of prediction to illustrate critical areas of conceptual and pragmatic overlap. Specifically, we focus on an ecological perspective to envision a research pipeline that connects these different scales of data and predictions from the aims of discovery to intervention. Pathogen discovery and predictions focused at the phylogenetic scale can first provide coarse and pattern-based guidance for which reservoirs, vectors and pathogens are likely to be involved in spillover, thereby narrowing surveillance targets and where such efforts should be conducted. Next, these predictions can be followed with ecologically driven spatio-temporal studies of reservoirs and vectors to quantify spatio-temporal fluctuations in infection and to mechanistically understand how pathogens circulate and are transmitted to humans. This approach can also help identify general regions and periods for which spillover is most likely. We illustrate this point by highlighting several case studies where long-term, ecologically focused studies (e.g. Lyme disease in the northeast USA, Hendra virus in eastern Australia, Plasmodium knowlesi in Southeast Asia) have facilitated predicting spillover in space and time and facilitated the design of possible intervention strategies. Such studies can in turn help narrow human surveillance efforts and help refine and improve future large-scale, phylogenetic predictions. We conclude by discussing how greater integration and exchange between data and predictions generated across these varying scales could ultimately help generate more actionable forecasts and interventions

Climate change could increase the geographic extent of Hendra virus spillover risk

Disease risk mapping is important for predicting and mitigating impacts of bat-borne viruses, including Hendra virus (Paramyxoviridae:Henipavirus), that can spillover to domestic animals and thence to humans. We produced two models to estimate areas at potential risk of HeV spillover explained by the climatic suitability for its flying fox reservoir hosts, Pteropus alecto and P. conspicillatus. We included additional climatic variables that might affect spillover risk through other biological processes (such as bat or horse behaviour, plant phenology and bat foraging habitat). Models were fit with a Poisson point process model and a log-Gaussian Cox process. In response to climate change, risk expanded southwards due to an expansion of P. alecto suitable habitat, which increased the number of horses at risk by 175–260% (110,000–165,000). In the northern limits of the current distribution, spillover risk was highly uncertain because of model extrapolation to novel climatic conditions. The extent of areas at risk of spillover from P. conspicillatus was predicted shrink. Due to a likely expansion of P. alecto into these areas, it could replace P. conspicillatus as the main HeV reservoir. We recommend: (1) HeV monitoring in bats, (2) enhancing HeV prevention in horses in areas predicted to be at risk, (3) investigate and develop mitigation strategies for areas that could experience reservoir host replacements