Formazanate Complexes of Hypervalent Group‐14 Elements as Precursors to Electronically Stabilized Radicals

The stability of molecular radicals containing main‐group elements usually hinges on the presence of bulky substituents that shield the reactive radical center. We describe a family of group‐14 formazanate complexes whose chemical reduction allows access to radicals that are stabilized instead by geometric and electron‐delocalization effects, specifically by the square‐pyramidal geometry adopted by the group‐14 atom (Si, Ge, Sn) within the framework of the heteroatom‐rich formazanate ligands. The reduction potentials of the Si, Ge, and Sn complexes as determined by cyclic voltammetry become more negative in that order. Examination of the solid‐state structures of these complexes suggested that their electron‐accepting ability decreases with increasing group‐14 atom size because a larger central atom increases the nonplanarity of the ligand‐based conjugated π‐electron system of the complex. The experimental findings were supported by density‐functional calculations on the parent complexes and the corresponding radicals

The sensitivity of primary productivity in Disko Bay, a coastal Arctic ecosystem, to changes in freshwater discharge and sea ice cover

The Greenland ice sheet is melting, and the rate of ice loss has increased 6-fold since the 1980s. At the same time, the Arctic sea ice extent is decreasing. Meltwater runoff and sea ice reduction both influence light and nutrient availability in the coastal ocean, with implications for the timing, distribution, and magnitude of phytoplankton production. However, the integrated effect of both glacial and sea ice melt is highly variable in time and space, making it challenging to quantify. In this study, we evaluate the relative importance of these processes for the primary productivity of Disko Bay, west Greenland, one of the most important areas for biodiversity and fisheries around Greenland. We use a high-resolution 3D coupled hydrodynamic–biogeochemical model for 2004–2018 validated against in situ observations and remote sensing products. The model-estimated net primary production (NPP) varied between 90–147 gC m−2 yr−1 during 2004–2018, a period with variable freshwater discharges and sea ice cover. NPP correlated negatively with sea ice cover and positively with freshwater discharge. Freshwater discharge had a strong local effect within ∼ 25 km of the source-sustaining productive hot spots during summer. When considering the annual NPP at bay scale, sea ice cover was the most important controlling factor. In scenarios with no sea ice in spring, the model predicted a ∼ 30 % increase in annual production compared to a situation with high sea ice cover. Our study indicates that decreasing ice cover and more freshwater discharge can work synergistically and will likely increase primary productivity of the coastal ocean around Greenland.publishedVersio

Aluminum Complexes of N2O23‒ Formazanate Ligands Supported by Phosphine Oxide Donors

The synthesis and characterization of a new family of phosphine-oxide-supported aluminum formazanate complexes (7a, 7b, 8a, 9a) are reported. X-ray diffraction studies revealed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N2O23‒ formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ~ 30,000 M‒1 cm‒1) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density-functional theory. With the exception of 3-cyano substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are non-emissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of ‒0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between ‒1.34 and ‒1.75 V. When combined with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound

Process evaluation in the field: global learnings from seven implementation research hypertension projects in low-and middle-income countries

Background Process evaluation is increasingly recognized as an important component of effective implementation research and yet, there has been surprisingly little work to understand what constitutes best practice. Researchers use different methodologies describing causal pathways and understanding barriers and facilitators to implementation of interventions in diverse contexts and settings. We report on challenges and lessons learned from undertaking process evaluation of seven hypertension intervention trials funded through the Global Alliance of Chronic Diseases (GACD). Methods Preliminary data collected from the GACD hypertension teams in 2015 were used to inform a template for data collection. Case study themes included: (1) description of the intervention, (2) objectives of the process evaluation, (3) methods including theoretical basis, (4) main findings of the study and the process evaluation, (5) implications for the project, policy and research practice and (6) lessons for future process evaluations. The information was summarized and reported descriptively and narratively and key lessons were identified. Results The case studies were from low- and middle-income countries and Indigenous communities in Canada. They were implementation research projects with intervention arm. Six theoretical approaches were used but most comprised of mixed-methods approaches. Each of the process evaluations generated findings on whether interventions were implemented with fidelity, the extent of capacity building, contextual factors and the extent to which relationships between researchers and community impacted on intervention implementation. The most important learning was that although process evaluation is time consuming, it enhances understanding of factors affecting implementation of complex interventions. The research highlighted the need to initiate process evaluations early on in the project, to help guide design of the intervention; and the importance of effective communication between researchers responsible for trial implementation, process evaluation and outcome evaluation. Conclusion This research demonstrates the important role of process evaluation in understanding implementation process of complex interventions. This can help to highlight a broad range of system requirements such as new policies and capacity building to support implementation. Process evaluation is crucial in understanding contextual factors that may impact intervention implementation which is important in considering whether or not the intervention can be translated to other contexts

Educação para pensar questões socioambientais e qualidade de vida

A análise das relações entre educação e condições de saúde nos grandes centros urbanos está definitivamente atrelada às questões socioambientais. Pensar qualidade de vida significa pensar qualidade ambiental e desenvolver ações preventivas de saúde pressupõe voltar olhos para o crescimento urbano. O presente trabalho trata da causalidade de condições de baixa qualidade de vida e saúde advinda das mudanças de paisagem e problemas ambientais associados ao crescimento urbano desordenado. Apresenta ainda uma análise crítica dos condicionantes da acomodação em situações de inadequação ambiental e baixa qualidade de vida, apontando para possíveis formas como a educação ambiental pode significar o instrumento pelo qual a comunidade se abra à reflexão sobre o lugar habitado e o tratamento das questões socioambientais nele vivenciadas. As bases para pensar essa educação passam pela abordagem crítica e sócioconstrutivista e os pressupostos da educação ambiental

Guía para la interpretación penal de delitos en comunidades

Curso de Especial Interés: Perfilación Criminal Aplicada a la Investigación del Delito ViolentoEl presente trabajo tiene como finalidad la realización de una guía para la interpretación de delitos en comunidades indígenas mediante un comparativo entre la jurisdicción ordinaria colombiana y la jurisdicción especial indígena, como bien se sabe la administración de justicia en Colombia se constituye en una función Pública e independiente. Este producto promete ser el primero en su categoría, proporcionando a los usuarios una guía práctica.Resumen 1. Objetivos 2. Marco teórico- histórico 3. Marco legal 4. Marco ético 5. Objetivos 6. Resultados Conclusiones ReferenciasPregradoPsicólog