To devise a reliable strategy for achieving specific HOMO and LUMO energy level modulation via alternating donor‐acceptor monomer units, we investigate a series of conjugated polymers (CPs) in which the electron withdrawing power of the acceptor group is varied, while maintaining the same donor group and the same conjugated chain conformation. Through experiment and DFT calculations, good correlation is identified between the withdrawing strength of the acceptor group, the HOMO and LUMO levels, and the degree of orbital localization, which allows reliable design principles for CPs. Increasing the acceptor strength results in an enhanced charge transfer upon combination with a donor monomer and a more pronounced decrease of the LUMO level. Moreover, while HOMO states remain delocalized along the polymer chain, LUMO states are strongly localized at specific bonds within the acceptor group. The degree of LUMO localization increases with increasing polymer length, which results in a further drop of the LUMO level and converges to its final value when the number of repeat units reaches the characteristic conjugation length. Based on these insights we designed PBT8PT, which exhibits 6.78% power conversion efficiency after device optimization via the additive assisted annealing, demonstrating the effectiveness of our predictive design approach.
Purpose. The Quebec Longitudinal Study of Child Development (QLSCD) was designed to examine the long-term associations of preschool physical, cognitive, social, and emotional development with biopsychosocial development across childhood, adolescence, and young adulthood.Methods. QLSCD is an ongoing prospective cohort including 2120 singletons born in 1997/1998 in the Canadian province of Quebec. So far, data has been collected annually or every two years from child ages 5 months to 21 years. The cohort currently includes 1245 participants. Data available include a range of environmental (e.g., family characteristics, child behaviour, educational attainment, mental health), biological (e.g., hair cortisol, genetic, epigenetic), and administrative data.Results. QLSCD has contributed to the understanding of children's psychosocial development, including the development of physical aggression and anxiety. QLSCD articles have advanced scientific knowledge on the influence of early childhood factors on childhood, adolescent, and young adult mental health, including the effect of participation in early childcare on cognitive and behavioural development, the developmental origins of adolescent and young adult mental health problems and suicide risk, and the development of interpersonal difficulties (e.g., peer victimisation) from preschool years to adolescence. Conclusion.QLSCD has given major contributions to our understanding of the link between different aspects of child development and biopsychosocial development during the first two decades of life. Unique features include the presence of environmental, biological, and administrative data, long-term follow-up with frequent data collections, and use of data from multiple informants, including teachers, mothers, fathers, and the children themselves.
ObjectiveTo evaluate radiologic and clinical inflammatory activity in women with MS during pregnancy and postpartum.MethodsWe performed a retrospective analysis of prospectively collected clinical and MRI reports for women who became pregnant while followed at the University of California, San Francisco MS Center between 2005 and 2018. Proportion of brain MRIs with new T2-hyperintense or gadolinium enhancing (Gd+) lesions (primary outcome) and annualized relapse rate (ARR; secondary) were compared before and after pregnancy.ResultsWe identified 155 pregnancies in 119 women (median Expanded Disability Status Scale [EDSS] 2.0). For the 146 live birth pregnancies, prepregnancy ARR was 0.33; ARR decreased during pregnancy, particularly the third trimester (ARR 0.10, p = 0.017) and increased in the 3 months postpartum (ARR 0.61, p = 0.012); and 16% of women experienced a clinically meaningful increase in EDSS. Among 70 pregnancies with paired brain MRIs available, 53% had new T2 and/or Gd+ lesions postpartum compared with 32% prepregnancy (p < 0.001). Postpartum clinical relapses were associated with Gd+ lesions (p < 0.001). However, even for patients without postpartum relapses, surveillance brain MRIs revealed new T2 and/or Gd+ lesions in 31%. Protective effects of exclusive breastfeeding for ≥3 months (odds ratio = 0.3, 95% confidence interval 0.1–0.9) were observed for relapses.ConclusionsBuilding on previous reports of increased relapse rate in the first 3 months postpartum, we report a significant association between inflammation on MRI and this clinical activity. We also detected postpartum radiologic activity in the absence of relapses. Both clinical and radiologic reassessment may inform optimal treatment decision-making during the high-risk early postpartum period.
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