Pi-pi to full ci: cation dimers and substituent effects in noncovalent interactions

The following thesis focuses on two areas of chemistry, pi-pi interactions and radical cation dimers. Approximations to the exact solution to the Schrodinger equation are investigated for these types of chemical systems with a variety of theoretical methods. The first chapter provides an introduction to the various quatum mechanical methods used in this research. The second chapter focuses specifically on pi-pi interaction. In this chapter, high quality quantum mechanical methods are used to examine how substituents tune pi-pi interactions between monosubstituted benzene dimers in parallel-displaced geometries. In addition, the role of dispersion and coulombic interactions in these systems is investigated to determine the nature of the substituent effect. In the third chapter radical cation dimers are investigated. Benchmark results with full configuration interaction (FCI) and equation-of-motion coupled-cluster for ionized systems (EOM-IP-CCSD) are presented for prototypical charge transfer species. Conclusions regarding chapters 2 and 3 are presented in the final chapter. This work may form the basis for improved approaches to rational drug design, organic optical materials, and molecular electronics.M.S.Committee Chair: Sherrill, C. David; Committee Member: Bredas, Jean-Luc; Committee Member: Hud, Nicholas; Committee Member: Perry, Josep

The hospital anxiety and depression rating scale: A cross-sectional study of psychometrics and case finding abilities in general practice

BACKGROUND: General practitioners' (GPs) diagnostic skills lead to underidentification of generalized anxiety disorders (GAD) and major depressive episodes (MDE). Supplement of brief questionnaires could improve the diagnostic accuracy of GPs for these common mental disorders. The aims of this study were to examine the usefulness of The Hospital Anxiety and Depression Rating Scale (HADS) for GPs by: 1) Examining its psychometrics in the GPs' setting; 2) Testing its case-finding properties compared to patient-rated GAD and MDE (DSM-IV); and 3) Comparing its case finding abilities to that of the GPs using Clinical Global Impression-Severity (CGI-S) rating. METHODS: In a cross-sectional survey study 1,781 patients in three consecutive days in September 2001 attended 141 GPs geographically spread in Norway. Sensitivity, specificity, optimal cut off score, and Area under the curve (AUC) for the HADS and the CGI-S were calculated with Generalized Anxiety Questionnaire (GAS-Q) as reference standard for GAD, and Depression Screening Questionnaire (DSQ) for MDE. RESULTS: The HADS-A had optimal cut off ≥8 (sensitivity 0.89, specificity 0.75), AUC 0.88 and 76% of patients were correctly classified in relation to GAD. The HADS-D had by optimal cut off ≥8 (sensitivity 0.80 and specificity 0.88) AUC 0.93 and 87% of the patients were correctly classified in relation to MDE. Proportions of the total correctly classified at the CGI-S optimal cut-off ≥3 were 83% of patients for GAD and 81% for MDE. CONCLUSION: The results indicate that addition of the patients' HADS scores to GPs' information could improve their diagnostic accuracy of GAD and MDE

Bridging the gap between clinicians and fitness professionals

Objective Health clubs (HC) and personal trainers (PT) are traditional outlets for the promotion of physical activity (PA) and exercise programming. As physicians are increasingly being called on to write exercise prescriptions for their patients, this study sought to investigate the level of integration between the healthcare and fitness systems. Design An internet study was designed with five domains to understand physicians’: (1) overall perception of HC, (2) appropriateness and recommendation of HC and PT to their patients, (3) attitude regarding specific aspects of HC, (4) support of patient participation in HC sponsored exercise and (5) elements of HC that physicians would like to know for referral. Methods An electronic survey was sent to members of two mailing lists of primary care and sports medicine specialty physicians during 2011–2012. Results On a Likert scale of 1–10 412 physicians reported being familiar with HC (8.9±2.1), indicated a favourable view of HC (7.9±2.2), and believe HC to be an appropriate venue for their patients (7.5±2.3). However, physicians only recommend HC to 41%±28% of their patients and PT for only 21%±21.6% of patients. Physicians ranked expense and convenience as the most problematic elements of HC (8.1±2.1 and 6.3±2.5, respectively). 72% of physicians indicated cost as most concerning when recommending a specific HC. Conclusion HC and PT are a significant implementation system for the promotion of physical activity, yet physicians are concerned with several elements of HC and are not adequately relying on this partnership to promote physical activity to their patients

Sleep-Wake Patterns during the Acute Phase after First-Ever Stroke

This study describes the pattern of day and night sleep and explores relationships between these patterns and sociodemographic and clinical factors as well as sleep environmental context and the patient's subjective sleep quality. Data from 110 patients with first-ever stroke was collected by structured interview surveys, medical record, and objective estimated sleep data from wrist actigraphy. The variability in estimated sleep is large. Half the patients slept either <6 hours or >8 hours per night, and 78% had more than nine awakenings per night. Men slept less than women, and patients sleeping at home had fewer awakenings than those who slept in hospital. It was estimated sleep during daytime in all, except 4, patients. Longer stay in hospital was related to more daytime sleep, and the subjective sleep quality correlated with estimated sleep time, wake time, and wake percentage

The Course of Fatigue during the First 18 Months after First-Ever Stroke: A Longitudinal Study

Background. Little is known about the course of poststroke fatigue. Objectives. To describe the course of poststroke fatigue in relation to the patient's level of physical functioning, depressive symptoms, and self-reported history of prestroke fatigue. Methods. A longitudinal study using structured face-to-face interviews, questionnaires, and patients' medical records. Data were collected from 95 patients in Norway with first-ever stroke. Fatigue was measured with the Fatigue Severity Scale 7 item version and assessed for change between the acute phase, six, 12, and 18 months after stroke using 2-way ANOVA repeated-measures analyses. Results. The patients' level of fatigue did not change over time. However, those who reported prestroke fatigue showed a relatively high level of fatigue over time in the poststroke period, while patients with no history of pre-stroke fatigue showed a stable course of relatively low fatigue over time. Conclusion. Studies on poststroke fatigue should control for the patient's pre-stroke fatigue level

Emotion regulation in patients with rheumatic diseases: validity and responsiveness of the Emotional Approach Coping Scale (EAC)

Background Chronic rheumatic diseases are painful conditions which are not entirely controllable and can place high emotional demands on individuals. Increasing evidence has shown that emotion regulation in terms of actively processing and expressing disease-related emotions are likely to promote positive adjustment in patients with chronic diseases. The Emotional Approach Coping Scale (EAC) measures active attempts to acknowledge, understand, and express emotions. Although tested in other clinical samples, the EAC has not been validated for patients with rheumatic diseases. This study evaluated the data quality, internal consistency reliability, validity and responsiveness of the Norwegian version of the EAC for this group of patients. Methods 220 patients with different rheumatic diseases were included in a cross-sectional study in which data quality and internal consistency were assessed. Construct validity was assessed through comparisons with the Brief Approach/Avoidance Coping Questionnaire (BACQ) and the General Health Questionnaire (GHQ-20). Responsiveness was tested in a longitudinal pretest-posttest study of two different coping interventions, the Vitality Training Program (VTP) and a Self-Management Program (SMP). Results The EAC had low levels of missing data. Results from principal component analysis supported two subscales, Emotional Expression and Emotional Processing, which had high Cronbach's alphas of 0.90 and 0.92, respectively. The EAC had correlations with approach-oriented items in the BACQ in the range 0.17-0.50. The EAC Expression scale had a significant negative correlation with the GHQ-20 of -0.13. As hypothesized, participation in the VTP significantly improved EAC scores, indicating responsiveness to change. Conclusion The EAC is an acceptable and valid instrument for measuring emotional processing and expression in patients with rheumatic diseases. The EAC scales were responsive to change in an intervention designed to promote emotion regulation. The instrument has not yet been tested for test-retest reliability, which is recommended in future studies