Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.

Measured parental weight status and familial socio-economic status correlates with childhood overweight and obesity at age 9

Background: Parental obesity is a predominant risk factor for childhood obesity. Family factors including socio-economic status (SES) play a role in determining parent weight. It is essential to unpick how shared family factors impact on child weight. This study aims to investigate the association between measured parent weight status, familial socio-economic factors and the risk of childhood obesity at age 9. Methodology/Principal Findings: Cross sectional analysis of the first wave (2008) of the Growing Up in Ireland (GUI) study. GUI is a nationally representative study of 9-year-old children (N = 8,568). Schools were selected from the national total (response rate 82%) and age eligible children (response rate 57%) were invited to participate. Children and their parents had height and weight measurements taken using standard methods. Data were reweighted to account for the sampling design. Childhood overweight and obesity prevalence were calculated using International Obesity Taskforce definitions. Multinomial logistic regression examined the association between parent weight status, indicators of SES and child weight. Overall, 25% of children were either overweight (19.3%) or obese (6.6%). Parental obesity was a significant predictor of child obesity. Of children with normal weight parents, 14.4% were overweight or obese whereas 46.2% of children with obese parents were overweight or obese. Maternal education and household class were more consistently associated with a child being in a higher body mass index category than household income. Adjusted regression indicated that female gender, one parent family type, lower maternal education, lower household class and a heavier parent weight status significantly increased the odds of childhood obesity. Conclusions/Significance: Parental weight appears to be the most influential factor driving the childhood obesity epidemic in Ireland and is an independent predictor of child obesity across SES groups. Due to the high prevalence of obesity in parents and children, population based interventions are required.

Development of a dissolvable microneedle influenza vaccine patch

Delivery of large molecular weight biological molecules to the epidermis and dermis is constrained by the tough outer layer of the epidermis, the stratum corneum (sc). Microneedle technologies attempt to overcome this physical barrier using sharp micron-size projections to penetrate the sc. Dissolvable microneedles (DMN), are a particular microneedle design whereby the needle structure is composed of a soluble matrix that upon application to the skin, dissolves releasing the vaccine load into skin. This thesis examines (1) the formulation and processing considerations around DMN fabrication, (2) the immunogenicity of DMN containing trivalent influenza vaccine (TIV) in pre-clinical mouse and pig models and (3) the thermostability of these DMN formulations during storage. The results demonstrate the importance of formulation for microneedle formation and mechanical strength. Trehalose and polyvinylalcohol based formulations produced optimal microneedle structures and were amenable to piezoelectric dispensing; allowing for precise multi-layered DMN to be fabricated. The effect of drying conditions was assessed and found to be critical for DMN mechanical strength and skin penetration. The antibody responses to TIV generated by DMN-mediated vaccination were comparable or greater to those induced by immunization with a commercial TIV via the IM route in mice. DMN mediated immunisation resulted in a significantly broader humoral response to heterotypic influenza viruses compared to IM delivery. Stored at 40°C, a licensed seasonal influenza vaccine incorporated into DMN array was thermostable for at least 6 month as determined by Single Radial Immunodiffusion and immunogenicity in mice. The thesis advances the field of DMN influenza vaccination by elucidating important processing and formulation considerations in the fabrication of highly reproducible DMN. It also demonstrated that DMN can induce broader, larger humoral responses than conventional IM administration while demonstrating enhanced accelerated stability. Crucially, this works advances an automated fabrication system that will allow for clinical translation of DMN.

Hazardous alcohol consumption among university students in Ireland: a cross-sectional study

Objective: There is considerable evidence of a cultural shift towards heavier alcohol consumption among university students, especially women. The aim of this study is to investigate the prevalence and correlates of hazardous alcohol consumption (HAC) among university students with particular reference to gender and to compare different modes of data collection in this population. Setting: A large Irish university. Design: A cross-sectional study using a classroom distributed paper questionnaire. Participants: A total of 2275 undergraduates completed the classroom survey, 84% of those in class and 51% of those registered for the relevant module. Main outcome measures: Prevalence of HAC measured using the Alcohol Use Disorders Identification Test for Consumption (AUDIT-C) and the proportion of university students reporting 1 or more of 13 adverse consequences linked to HAC. HAC was defined as an AUDIT-C score of 6 or more among males and 5 or more among females. Results: In the classroom sample, 66.4% (95% CI 64.4 to 68.3) reported HAC (65.2% men and 67.3% women). In women, 57.4% met HAC thresholds for men. Similar patterns of adverse consequences were observed among men and women. Students with a hazardous consumption pattern were more likely to report smoking, illicit drug use and being sexually active. Conclusions: The findings highlight the high prevalence of HAC among university students relative to the general population. Public policy measures require review to tackle the short-term and long-term risks to physical, mental and social health and well-being.