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Perylene diimides and related compounds (naphthalene diimides, anthracene diimides, etc.) are one of the most important classes of organic dyes. Therefore, the prediction and the rationalization of both their transition energies and the particular shape of their absorption and emission spectra is essential to improve their design. Here, we report the simulations of both adiabatic and vibronic signatures of a series of perylene diimide derivatives with a state-of-the-art time-dependent density functional theory (TD-DFT) approach. First, the 0–0 energies have been computed and compared to experimental data. In a second stage, the determination of vibronic shapes has been performed to shed light on the vibrational modes implied in the experimental band topologies. Both anharmonicity and functionnal effects are also discussed. It turns out that theory consistently reproduced 0–0 energies but does not always yield band shapes in perfect match with experiment. In a last stage, new structures are designed, and it is shown that a full push effect is more effective than a push–pull strategy for the present class of molecules

Not just a number: examining coverage and content of antenatal care in low-income and middle-income countries.

Introduction: Antenatal care (ANC) provides a critical opportunity for women and babies to benefit from good-quality maternal care. Using 10 countries as an illustrative analysis, we described ANC coverage (number of visits and timing of first visit) and operationalised indicators for content of care as available in population surveys, and examined how these two approaches are related. Methods: We used the most recent Demographic and Health Survey to analyse ANC related to women's most recent live birth up to 3 years preceding the survey. Content of care was assessed using six components routinely measured across all countries, and a further one to eight additional country-specific components. We estimated the percentage of women in need of ANC, and using ANC, who received each component, the six routine components and all components. Results: In all 10 countries, the majority of women in need of ANC reported 1+ ANC visits and over two-fifths reported 4+ visits. Receipt of the six routine components varied widely; blood pressure measurement was the most commonly reported component, and urine test and information on complications the least. Among the subset of women starting ANC in the first trimester and receiving 4+ visits, the percentage receiving all six routinely measured ANC components was low, ranging from 10% (Jordan) to around 50% in Nigeria, Nepal, Colombia and Haiti. Conclusion: Our findings suggest that even among women with patterns of care that complied with global recommendations, the content of care was poor. Efficient and effective action to improve care quality relies on development of suitable content of care indicators

Granzyme B enters the mitochondria in a Sam50-, Tim22- and mtHsp70-dependent manner to induce apoptosis

We have found that granzyme B (GB)-induced apoptosis also requires reactive oxygen species resulting from the alteration of mitochondrial complex I. How GB, which does not possess a mitochondrial targeting sequence, enter this organelle is unknown. We show that GB enters the mitochondria independently of the translocase of the outer mitochondrial membrane complex, but requires instead Sam50, the central subunit of the sorting and assembly machinery that integrates outer membrane β- barrel proteins. Moreover, GB breaches the inner membrane through Tim22, the metabolite carrier translocase pore, in a mitochondrial heat-shock protein 70 (mtHsp70)-dependent manner. Granzyme A (GA) and caspase-3 use a similar route to the mitochondria. Finally, preventing GB from entering the mitochondria either by mutating lysine 243 and arginine 244 or depleting Sam50 renders cells more resistant to GB-mediated reactive oxygen species and cell death. Similarly, Sam50 depletion protects cells from GA-, GM- and caspase-3-mediated cell death. Therefore, cytotoxic molecules enter the mitochondria to induce efficiently cell death through a noncanonical Sam50-, Tim22- and mtHsp70-dependent import pathway

Observations sur diverses dispositions de la réforme de droit des contrats

Rapport remis à la Chancellerie dans le cadre de la consultation publique ouverte par le ministère de la justice sur le projet d'ordonnance portant réforme du droit des contrats, du régime général et de la preuve des obligations