Intramolecular surfaces for vicinal proton–proton coupling constants 3JHH

Equations for the intramolecular surfaces of the 3JHH coupling constants in ethane, ethylene, and acetylene are formulated, and the corresponding coefficients are estimated from calculations at the DFT/B3LYP level. The chosen variables are changes in bond lengths, in the torsion angle φ between the coupled protons Ha and Hb, in bond angles, and in dihedral angles. The 3JHH surface of ethane is formulated as an extended Karplus equation with the coefficients of a truncated Fourier series on the torsion angle φ expanded as second-order Taylor series in the chosen variables taking into account the invariance of 3JHH under reflections and rotations of nuclear coordinates. Partial vibrational contributions from linear and square terms corresponding to changes in the geometry of the Ha − Ca − Cb − Hb fragment are important while those from cross terms are small with a few exceptions. The 3JHH surface of ethane is useful to predict contributions to 3JHH from changes in local geometry of derivatives but vibrational contributions are predicted less satisfactorily. The predicted values at the B3LYP/BS2 level of the 3JHH couplings (vibrational contributions at 300 K) from equilibrium geometries are 9.79 (−0.17) for acetylene, and 17.08 (1.93) and 10.73(0.93) for the trans and cis couplings of ethylene.

Propriedades estruturais e eletrônicas de nanofilmes de TiO2 anatase: cálculos B3LYP-D* em sistemas periódicos bidimensionais

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Reducing the global burden of depression : population level analysis of intervention cost-effectiveness in 14 world regions

International evidence on the cost and effects of interventions for reducing the global burden of depression remain scarce. Aims: To estimate the population-level cost-effectiveness of evidence-based depression interventions and their contribution towards reducing current burden. Method: Primary-care-based depression interventions were modelled at the level of whole populations in 14 epidemiological subregions of the world. Total population-level costs (in international dollars or I$) and effectiveness (disability adjusted life years (DALYs) averted) were combined to form average and incremental cost-effectiveness ratios. Results: Evaluated interventions have the potential to reduce the current burden of depression by 10–30%. Pharmacotherapy with older antidepressant drugs, with or without proactive collaborative care, are currently more cost-effective strategies than those using newer antidepressants, particularly in lower-income subregions. Conclusions: Even in resource-poor regions, each DALYaverted by efficient depression treatments in primary care costs less than 1 year of average per capita income, making such interventions a cost-effective use of health resources. However, current levels of burden can only be reduced significantlyif there is a substantialincrease substantial increase intreatment coverage.

Moderation as judgement practice: Reconciling system level accountability and local level practice

Internationally, recognition of the role of assessment to inform the learning process has received much attention in recent years. Assessment for learning, not just of learning is being supported by an increasing body of literature providing strategies that teachers and their students can incorporate to support the learning process (Assessment Reform Group, 2002; Broadfoot & Black, 2004; James, 2006). Concurrently there has been an increase internationally in systemic accountability requirements of schools in terms of student results. The convergence of these two movements has resulted in some education systems promoting standards-driven reform involving authentic assessment and a re-examination of the relationship between the teacher and the student in the learning process. In this context standards are intended to be used as the basis for judgements of student achievement; while the results from assessment tasks are meant to both inform the teaching/learning process, and to report and track student progress. In such system, the role and reliability of teacher judgement takes centre stage.