Excited State Anions in Organic Transformations. Photoangeregte Anionen in organischen Reaktionen

Utilizing light is a smart way to fuel chemical transformations as it allows to selectively focus the energy on certain molecules. Many reactions involving electronically excited species proceed via open‐shell intermediates enabling novel and unique routes to expand the hitherto used synthetic toolbox in organic chemistry. The direct conversion of non‐prefunctionalized, less activated compounds is a highly desirable goal to pave the way towards a more sustainable and atom‐economic chemistry. Photoexcited closed‐shell anions have been shown to reach extreme potentials in single electron transfer reactions and reveal unusual excited state reactivity. It is therefore surprising, that their use as reagent or as photocatalyst is limited to a few examples. In this review, we briefly discuss the characteristics of anionic photochemistry, highlight pioneering work and show recent progress which has been made by utilizing photoexcited anionic species in organic synthesis

A Pilot Study on Dietary Approaches in Multiethnicity: Two Methods Compared

Background. Medical nutritional therapy is the most important method for normalizing glucose levels in pregnancy. In this setting, there is a new problem to consider relating to migrants, their personal food preferences, and ethnic, cultural, and religious aspects of their diet. We compared maternal and fetal outcomes between two multiethnic groups of pregnant women, one adopting a food plan that included dishes typical of the foreign women's original countries (the “ethnic meal plan” group), while the other group adopted a standard meal plan. Findings. To develop the meal plan, each dish chosen by the women was broken down into its principal ingredients. The quantity of each food was given in tablespoons, teaspoons, slices, and cups, and there were photographs of the complete dish. The group treated with the ethnic meal plan achieved a better metabolic control at the end of the pregnancy and a lower weight gain (though the difference was not statistically significant). As for fetal outcome, the group on the ethnic meal plan had babies with a lower birth weight and there were no cases of macrosomia or LGA babies. Conclusions. This preliminary study indicates the positive effect of an ethnic approach to diet on the outcome of pregnancy

Exploiting natural polysaccharides to enhance in vitro bio-constructs of primary neurons and progenitor cells

Current strategies in Central Nervous System (CNS) repair focus on the engineering of artificial scaffolds for guiding and promoting neuronal tissue regrowth. Ideally, one should combine such synthetic structures with stem cell therapies, encapsulating progenitor cells and instructing their differentiation and growth. We used developments in the design, synthesis, and characterization of polysaccharide-based bioactive polymeric materials for testing the ideal composite supporting neuronal network growth, synapse formation and stem cell differentiation into neurons and motor neurons. Moreover, we investigated the feasibility of combining these approaches with engineered mesenchymal stem cells able to release neurotrophic factors. We show here that composite bio-constructs made of Chitlac, a Chitosan derivative, favor hippocampal neuronal growth, synapse formation and the differentiation of progenitors into the proper neuronal lineage, that can be improved by local and continuous delivery of neurotrophins. Statement of Significance In our work, we characterized polysaccharide-based bioactive platforms as biocompatible materials for nerve tissue engineering. We show that Chitlac-thick substrates are able to promote neuronal growth, differentiation, maturation and formation of active synapses. These observations support this new material as a promising candidate for the development of complex bio-constructs promoting central nervous system regeneration. Our novel findings sustain the exploitation of polysaccharide-based scaffolds able to favour neuronal network reconstruction. Our study shows that Chitlac-thick may be an ideal candidate for the design of biomaterial scaffolds enriched with stem cell therapies as an innovative approach for central nervous system repair

TRY plant trait database – enhanced coverage and open access

Plant traits - the morphological, anatomical, physiological, biochemical and phenological characteristics of plants - determine how plants respond to environmental factors, affect other trophic levels, and influence ecosystem properties and their benefits and detriments to people. Plant trait data thus represent the basis for a vast area of research spanning from evolutionary biology, community and functional ecology, to biodiversity conservation, ecosystem and landscape management, restoration, biogeography and earth system modelling. Since its foundation in 2007, the TRY database of plant traits has grown continuously. It now provides unprecedented data coverage under an open access data policy and is the main plant trait database used by the research community worldwide. Increasingly, the TRY database also supports new frontiers of trait‐based plant research, including the identification of data gaps and the subsequent mobilization or measurement of new data. To support this development, in this article we evaluate the extent of the trait data compiled in TRY and analyse emerging patterns of data coverage and representativeness. Best species coverage is achieved for categorical traits - almost complete coverage for ‘plant growth form’. However, most traits relevant for ecology and vegetation modelling are characterized by continuous intraspecific variation and trait–environmental relationships. These traits have to be measured on individual plants in their respective environment. Despite unprecedented data coverage, we observe a humbling lack of completeness and representativeness of these continuous traits in many aspects. We, therefore, conclude that reducing data gaps and biases in the TRY database remains a key challenge and requires a coordinated approach to data mobilization and trait measurements. This can only be achieved in collaboration with other initiatives

Association of kidney disease measures with risk of renal function worsening in patients with type 1 diabetes

Background: Albuminuria has been classically considered a marker of kidney damage progression in diabetic patients and it is routinely assessed to monitor kidney function. However, the role of a mild GFR reduction on the development of stage 653 CKD has been less explored in type 1 diabetes mellitus (T1DM) patients. Aim of the present study was to evaluate the prognostic role of kidney disease measures, namely albuminuria and reduced GFR, on the development of stage 653 CKD in a large cohort of patients affected by T1DM. Methods: A total of 4284 patients affected by T1DM followed-up at 76 diabetes centers participating to the Italian Association of Clinical Diabetologists (Associazione Medici Diabetologi, AMD) initiative constitutes the study population. Urinary albumin excretion (ACR) and estimated GFR (eGFR) were retrieved and analyzed. The incidence of stage 653 CKD (eGFR < 60 mL/min/1.73 m2) or eGFR reduction > 30% from baseline was evaluated. Results: The mean estimated GFR was 98 \ub1 17 mL/min/1.73m2 and the proportion of patients with albuminuria was 15.3% (n = 654) at baseline. About 8% (n = 337) of patients developed one of the two renal endpoints during the 4-year follow-up period. Age, albuminuria (micro or macro) and baseline eGFR < 90 ml/min/m2 were independent risk factors for stage 653 CKD and renal function worsening. When compared to patients with eGFR > 90 ml/min/1.73m2 and normoalbuminuria, those with albuminuria at baseline had a 1.69 greater risk of reaching stage 3 CKD, while patients with mild eGFR reduction (i.e. eGFR between 90 and 60 mL/min/1.73 m2) show a 3.81 greater risk that rose to 8.24 for those patients with albuminuria and mild eGFR reduction at baseline. Conclusions: Albuminuria and eGFR reduction represent independent risk factors for incident stage 653 CKD in T1DM patients. The simultaneous occurrence of reduced eGFR and albuminuria have a synergistic effect on renal function worsening

Light-triggered Catalytic Asymmetric Allylic Benzylation of Isatin-derived MBH Carbonates

The formation of new C-C bonds is among the most thriving fields of research in synthetic organic chemistry. In fact, novel C-C bond-forming transformations give access to new, unprecedented carbon backbones. An even more challenging goal is the development of synthetic methods able to forge quaternary all-carbon centres in an enantioselective fashion, that allow the synthesis of complex, valuable molecules like natural products. The growing attention to environment is now directing research towards greener chemical solutions: atom economy, environmentally friendly solvents, mild reaction conditions, and the use of renewable resources. Photochemistry and organocatalysis, the two co-protagonists of this thesis project, are in full agreement with the principles of Green Chemistry. The development of light-triggered transformations along with the employment of purely organic chiral catalysts allow milder reaction conditions, thus energy saving. This thesis project is focused on the development and the optimisation of the asymmetric allylic alkylation reaction, using non-stabilised, photo-generated nucleophiles. To the best of our knowledge, only very few examples of asymmetric allylic alkylation with non-stabilised nucleophiles have been reported, and none of them through an organocatalysed strategy. For this purpose, Morita-Baylis-Hillman (MBH) carbonates derived from isatin, a biologically active molecule, are selected as electrophiles. Starting from racemic MBH carbonates, quaternary all-carbon stereocentres are created in an enantioselective fashion via a dual activation strategy. The chiral organocatalyst activates the electrophile and is responsible for the stereoinduction event, while light irradiation activates the 2-methylbenzophenone derivative to form the photoenol intermediate as non-stabilised C-nucleophile. In addition, the reaction is also optimised under a microuidic photoreactor for in-flow continuous synthesis

Avaliação de tecidos moles e duros em implante com colo convergente usando a técnica de preparação biologicamente orientada (BOPT)

A capacidade do clínico e a seleção do tipo de implante é fundamental para o sucesso da reabilitação oral com implantes. Estudos recentes dedicam maior atenção à gestão de tecidos peri-implantares moles e duros, pois a sua estabilidade é parte integrante dos resultados de longo prazo. Alguns autores questionam se aumentando o espaço para os tecidos moles simulando a dentição natural, a sua estética e a manutenção dos tecidos duros pode ser otimizada. Baseando nesta teórica, desenvolveram-se os implantes com colo convergente que permitem uma nova abordagem para prótese, aproveitando as noções da técnica BOPT (técnica de preparação orientada biologicamente) desde a prótese em dentes naturais até aos implantes. Este tipo de implante também possui componentes convergentes para reabilitação implante-prótese que se voltam para a vantagem de tecidos duros, respeitando a biologia circundante, favorecendo a sua estabilidade para um resultado funcional ideal, aproveitando a vantagem de ter uma morfologia convergente. Foi realizada uma pesquisa bibliográfica na PUBMED usando uma combinação de palavras-chave: implante, BOPT, tecido mole, tecido duro, colo convergente. A pesquisa identificou 107 artigos, dos quais 15 foram levados em consideração. Esses estudos demonstram o objetivo da minha tese que é compreender se as reabilitações com implantes com colo convergente usando a técnica BOPT podem melhorar a estabilidade dos tecidos moles e duros peri-implanteares, nomeadamente a estética gengival, diminuição de sangramento à sondagem, aumento de volume e a altura da mucosa queratinizada e menos perda óssea

The sense of dignity and the risk of loss in cronic disease: Review of the literature

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A dinuclear copper(ii) complex with photoswitchable catechol oxidation activity

In this study, we report the first example of a photoswitchable copper complex with catechol oxidase activity. The distance between the two copper centres is optimal for catalytic catechol oxidation in the Z-configuration. Thus, the activity of the catalyst is increased compared to its E-configuration