Chemical Reaction Dynamics under Vibrational Strong Coupling

In this thesis, we use classical, semi-classical and quantum-mechanical methods to simulate chemical reaction dynamics inside of an optical cavity. Within such a cavity, by selectively coupling vibrational modes of the reactants to the vacuum state of light, recent experiments have observed significant changes in reaction rates and equilibrium constants - all without any external input of energy. We investigate the dynamics of both a single reaction and an ensemble of N identical reactions coupled to the cavity. In our single reactant studies, we find significant modification to the rate of reaction and to its quantum-mechanical equilibrium constant. All of the effects observed in our single molecule studies are however found to diminish as the number of reactants is increased. For any experimentally relevant number of molecules, the cavity effects on the reaction rate and the equilibrium constant are therefore shown to be negligible within all theories considered in this thesis. This thesis therefore does not offer any explanation for the experimental observations. It does however highlight issues with all current theoretical work on this topic, and provides suggestions - in light of the results presented here and in recent literature - as to what might be required to explain these effects.Comment: undergrad thesi

The ex-client’s experience of attitudinal and structural barriers to therapy, prior to and during the therapeutic relationship

People’s reluctance to seek/secure counselling/psychotherapy is an area requiring further attention. This study sought to add to existing research by undertaking phenomenological interviews exploring ex-clients experiences of seeking/securing help. Semi-structured, qualitative interviews were conducted with five participants who had experience of the counselling process. Transcribed interviews were analysed using the constant-comparative method and five themes emerged: public stigma, self-stigma, the counselling/psychotherapeutic environment, privacy/confidentiality, and waiting time to secure counselling. Results indicated public/self-stigma had affected participant experience, as had the counselling environment. Privacy/confidentiality was a concern with waiting times being less so. Recommendations to reduce the negative impact of public/self-stigma and the counselling environment are offered, as are areas requiring further research including advertising, location of service, self-stigma and home counselling/psychotherapy

Developing physical capability standards that are predictive of success on special forces selection courses

Free to read This study aimed to develop minimum standards for physical capability assessments (vertical jump, sit and reach, push-ups, seven-stage sit-ups, heaves, agility, 20-m shuttle run, loaded 5-km pack march, and 400-m swim) that candidates must pass before they can commence Australian Army Special Forces (SF) selection courses. Soldiers (Part A: n = 104; Part B: n = 92) completed the physical capability assessments before commencing a SF selection course. At the beginning of these selection courses, participants attempted two barrier assessments (3.2-km battle run and 20-km march). Statistical analysis revealed several physical capability assessments were associated with performance on the barrier assessments and selection course outcome (Part A); however, these statistical models were unable to correctly classify all candidates as likely to pass or fail the selection course. Alternatively, manual analysis identified a combination of physical capability standards that correctly classified 14% to 18% of candidates likely to fail, without excluding any candidates able to pass (Part A). The standards were applied and refined through Part B and included completing the 5-km pack march in ≤45:45 minutes : seconds, achieving ≥level five on the sit-up test, or completing ≥66 push-ups. Implementation of these standards may reduce attrition rates and enhance the efficiency of the SF recruitment process

Propagation of Pericentral Necrosis During Acetaminophen-Induced Liver Injury: Evidence for Early Interhepatocyte Communication and Information Exchange.

Acetaminophen (APAP)-induced liver injury is clinically significant, and APAP overdose in mice often serves as a model for drug-induced liver injury in humans. By specifying that APAP metabolism, reactive metabolite formation, glutathione depletion, and mitigation of mitochondrial damage within individual hepatocytes are functions of intralobular location, an earlier virtual model mechanism provided the first concrete multiattribute explanation for how and why early necrosis occurs close to the central vein (CV). However, two characteristic features could not be simulated consistently: necrosis occurring first adjacent to the CV, and subsequent necrosis occurring primarily adjacent to hepatocytes that have already initiated necrosis. We sought parsimonious model mechanism enhancements that would manage spatiotemporal heterogeneity sufficiently to enable meeting two new target attributes and conducted virtual experiments to explore different ideas for model mechanism improvement at intrahepatocyte and multihepatocyte levels. For the latter, evidence supports intercellular communication via exosomes, gap junctions, and connexin hemichannels playing essential roles in the toxic effects of chemicals, including facilitating or counteracting cell death processes. Logic requiring hepatocytes to obtain current information about whether downstream and lateral neighbors have triggered necrosis enabled virtual hepatocytes to achieve both new target attributes. A virtual hepatocyte that is glutathione-depleted uses that information to determine if it will initiate necrosis. When a less-stressed hepatocyte is flanked by at least two neighbors that have triggered necrosis, it too will initiate necrosis. We hypothesize that the resulting intercellular communication-enabled model mechanism is analogous to the actual explanation for APAP-induced hepatotoxicity at comparable levels of granularity

Representation of western disturbances in CMIP5 models

Western disturbances (WDs) are synoptic extratropical disturbances embedded in the subtropical westerly jet stream. They are an integral part of the South Asian winter climate, both for the agriculture-supporting precipitation they bring to the region and for the associated isolated extreme events that can induce devastating flash flooding. Here, WD behaviour and impacts are characterised in 23 CMIP5 historical simulations and compared with reanalysis and observations. It is found that WD frequency has a strong relationship with model resolution: higher resolution models produce significantly more WDs, and a disproportionately high fraction of extreme events. Exploring metrics of jet strength and shape, we find that the most probable cause of this relationship is that the jet is wider in models with coarser resolution, and therefore the northern edge in which WDs are spun up sits too far north of India. The frequency of WDs in both winter and summer is found to be overestimated by most models, and thus the winter frequency of WDs estimated from the multi-model mean (30 winter−1) is above the reanalysis mean (26 winter−1). In this case, the error cannot be adequately explained by local jet position and strength. Instead, we show that it is linked with a positive bias in upstream mid-tropospheric baroclinicity. Despite a positive winter precipitation bias in CMIP5 models over most of India and Pakistan and a dry bias in the western Himalaya, the fraction of winter precipitation for which WDs are responsible is accurately represented. Using partial correlation, it is shown that the overestimation in WD frequency is the largest contributor to this bias, with a secondary, spatially heterogeneous contribution coming from the overestimation of WD intensity

Falling trend of western disturbances in future climate simulations

Western disturbances (WDs) are synoptic-scale cyclonic weather systems advected over Pakistan and north India by the subtropical westerly jet stream. There, they are responsible for most of the winter precipitation, crucial for agriculture of the rabi crop, as well as more extreme precipitation events, which can lead to local flooding and avalanches. Despite their importance, there has not yet been an attempt to objectively determine the fate of WDs in future climate GCMs. Here, a tracking algorithm is used to build up a catalogue of WDs in both CMIP5 historical and representative concentration pathway (RCP) experiments of the future. It is shown that in business-as-usual (RCP8.5) future climate simulations, WD frequency falls by around 15% by the end of the twenty-first century, with the largest relative changes coming in pre- and post-monsoon months. Meanwhile, mean WD intensity will decrease, with central vorticity expected to become less cyclonic by about 12% over the same period. Changes in WD frequency are attributed to the projected widening and weakening of the winter subtropical jet; as well as decreasing meridional wind shear and mid-tropospheric baroclinic vorticity tendency, which also explain the changes in intensity. Finally, the impact of these changes on regional precipitation is explored. The decline in WD frequency and intensity will cause a decrease in mean winter rainfall over Pakistan and north India amounting to about 15% of the mean -- subject to the ability of the models to represent the processes responsible. The effect on extreme precipitation events, however, remains unclear

Characteristics of stable flows over Southern Greenland

The main characteristic features of stable atmospheric flows over a large mountain plateau are summarised and then compared with mesoscale and synoptic scale numerical simulation, meteorological analysis, satellite imagery, and surface observations for the cases of flows over Southern Greenland for four wind directions. The detailed features are identified using the concepts and scaling of stably stratified flow over large mountains with variations in surface roughness, elevation, and heating. For westerly and easterly winds detached jets form at the southern tip, where coastal jets converge, which propagate large distances across the ocean. Near coasts katabatic winds can combine with barrier jets and wake flows generated by synoptic winds. Note how the approach flow rises/falls over southern Greenland for easterly/westerly winds, leading in both cases to more cloud on the western side. Some conclusions are drawn about the large-scale influences of these flows; detached jets in the atmosphere; air-sea interaction; formation of low pressure systems. For accurate simulations of these flows, mesoscale models are necessary with resolutions of order of 20 km or less. © Birkhäuser Verlag, Basel, 2005

Pancreatic cysts suspected to be branch duct intraductal papillary mucinous neoplasm without concerning features have low risk for development of pancreatic cancer.

BackgroundThe risk of developing pancreatic cancer is uncertain in patients with clinically suspected branch duct intraductal papillary mucinous neoplasm (BD-IPMN) based on the "high-risk stigmata" or "worrisome features" criteria proposed in the 2012 international consensus guidelines ("Fukuoka criteria").MethodsRetrospective case series involving patients referred for endoscopic ultrasound (EUS) of indeterminate pancreatic cysts with clinical and EUS features consistent with BD-IPMN. Rates of pancreatic cancer occurring at any location in the pancreas were compared between groups of patients with one or more Fukuoka criteria ("Highest-Risk Group", HRG) and those without these criteria ("Lowest-Risk Group", LRG).ResultsAfter exclusions, 661 patients comprised the final cohort (250 HRG and 411 LRG patients), 62% female with an average age of 67 years and 4 years of follow up. Pancreatic cancer, primarily adenocarcinoma, occurred in 60 patients (59 HRG, 1 LRG). Prevalent cancers diagnosed during EUS, immediate surgery, or first year of follow up were found in 48/661 (7.3%) of cohort and exclusively in HRG (33/77, 42.3%). Using Kaplan-Meier method, the cumulative incidence of cancer at 7 years was 28% in HRG and 1.2% in LRG patients (P<0.001).ConclusionsThis study supports using Fukuoka criteria to stratify the immediate and long-term risks of pancreatic cancer in presumptive BD-IPMN. The risk of pancreatic cancer was highest during the first year and occurred exclusively in those with "high-risk stigmata" or "worrisome features" criteria. After the first year all BD-IPMN continued to have a low but persistent cancer risk