The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4

Funding Research was funded by Fundação para a Ciência e a Tecnologia (FCT): projects UIDB/00100/2020, UIDP/00100/2020, LA/P/0056/2020, UIDB/04046/2020, UIDP/04046/2020, UIDB/50006/2020, UIDP/50006/2020 and LA/P/0008/2020, UIDB/04378/2020, UIDP/04378/2020, and LA/P/0140/2020, PTDC/QUI-QFI/29236/2017, PTDCQUI-QIN0252_2021, CEECIND/00509/2017; Fonds de la Recherche Scientifique (FNRS): PDR T.0095.21); Portugal2020: CENTRO-01-0145-FEDER-000018; Royal Society of Chemistry (RSC): R21-7511142525. Acknowledgments Centro de Química Estrutural (CQE) and Institute of Molecular Sciences (IMS) acknowledge the financial support of Fundação para a Ciência e a Tecnologia (FCT): Projects UIDB/00100/2020, UIDP/00100/2020, and LA/P/0056/2020, respectively. BioISI acknowledges FCT for financial support (UIDB/04046/2020, UIDP/04046/2020). This work was supported by the FNRS (PDR T.0095.21). Clara S. B. Gomes acknowledges the Associate Laboratory for Green Chemistry—LAQV, the Applied Molecular Biosciences Unit—UCIBIO and Associated Laboratory i4HB, which are financed by national funds from FCT (UIDB/50006/2020, UIDP/50006/2020 and LA/P/0008/2020, UIDB/04378/2020 and UIDP/04378/2020, and LA/P/0140/2020, respectively). Sónia Barroso thanks project SmartBioR for financial support (CENTRO-01-0145-FEDER-000018)and Centro de Química Estrutural for the access to crystallography facilities. Nuno A. G. Bandeira gratefully acknowledges the NanoBioSolutions FCT grant PTDC/QUI-QFI/29236/2017 for the computational infrastructure. Paulo N. Martinho thanks FCT and RSC for financial support (grants PTDCQUI-QIN0252_2021 and R21-7511142525). Paulo N. Martinho also thanks FCT for the contract CEECIND/00509/2017.Complexes [Fe(X-salEen)2]BPh4·DMF, with X = Br (1), Cl (2), and F (3), were crystallised from N,N′-dimethylformamide with the aim of understanding the role of a high boiling point N,N′-dimethylformamide solvate in the spin crossover phenomenon. The counter ion was chosen for only being able to participate in weak intermolecular interactions. The compounds were structurally characterised by single crystal X-ray diffraction. Complex 1 crystallised in the orthorhombic space group P212121, and complexes 2 and 3 in the monoclinic space group P21/n. Even at room temperature, low spin was the predominant form, although complex 2 exhibited the largest proportion of the high-spin species according to both the magnetisation measurements and the Mössbauer spectra. Density Functional Theory calculations were performed both on the periodic solids and on molecular models for complexes 1–3 and the iodide analogue 4. While all approaches reproduced the experimental structures very well, the energy balance between the high-spin and low-spin forms was harder to reproduce, though some calculations pointed to the easier spin crossover of complex 2, as observed. Periodic calculations with the functional PBE led to very similar ΔEHS-LS values for all complexes but showed a preference for the low-spin form. However, the single-point calculations with B3LYP* showed, for the model without solvate, that the Cl complex should undergo spin crossover more easily. The molecular calculations also reflected this fact, which was more clearly defined when the cation–anion–solvate model was used. In the other models there was not much difference between the Cl, Br, and I complexes.publishersversionpublishe

Validity of a minimally invasive autopsy for cause of death determination in stillborn babies and neonates in Mozambique: an observational study

Background Over 5 million stillbirths and neonatal deaths occur annually. Limited and imprecise information on the cause of these deaths hampers progress in achieving global health targets. Complete diagnostic autopsies (CDAs) the gold standard for cause of death determination are difficult to perform in most high-burden settings. Therefore, validation of simpler and more feasible methods is needed. Methods and findings In this observational study, the validity of a minimally invasive autopsy (MIA) method in determining the cause of death was assessed in 18 stillbirths and 41 neonatal deaths by comparing the results of the MIA with those of the CDA. Concordance between the categories of diseases obtained by the 2 methods was assessed by the Kappa statistic, and the sensitivity, specificity, positive, and negative predictive values of the MIA diagnoses were calculated. A cause of death was identified in 16/18 (89%) and 15/18 (83%) stillborn babies in the CDA and the MIA, respectively. Fetal growth restriction accounted for 39%, infectious diseases for 22%, intrapartum hypoxia for 17%, and intrauterine hypoxia for 11% of stillborn babies. Overall, the MIA showed in this group a substantial concordance with the CDA (Kappa = 0.78, 95% CI [0.56-0.99]). A cause of death was identified in all (100%) and 35/41 (85%) neonatal deaths in the CDA and the MIA, respectively. In this group, the majority of deaths were due to infectious diseases (66%). The overall concordance of the MIA with the CDA in neonates was moderate (Kappa = 0.40, 95% CI [0.18-0.63]). A high percentage of accuracy was observed for the MIA in all the diagnostic categories in both stillbirths and neonates (>75%). The main limitation of this study is that some degree of subjective interpretation is inherent to cause-of-death attribution in both the MIA and the CDA; this is especially so in stillbirths and in relation to fetal growth restriction. Conclusions The MIA could be a useful tool for cause-of-death determination in stillbirths and neonatal deaths. These findings may help to accelerate progress towards meeting global health targets by obtaining more accurate information on the causes of death in these age groups, which is essential in guiding the design of new interventions and increasing the effectiveness of those already implemented

Contribution of the clinical information to the accuracy of the minimally invasive and the complete diagnostic autopsy

Although autopsy diagnosis includes routinely, a thorough evaluation of all available pathological results and also of any available clinical data, the contribution of this clinical information to the diagnostic yield of the autopsy has not been analyzed. We aimed to determine to which degree the use of clinical data improves the diagnostic accuracy of the complete diagnostic autopsy (CDA) and the minimally invasive autopsy (MIA), a simplified pathological postmortem procedure designed for low-income sites. 264 coupled MIA and CDA procedures (112 adults, 57 maternal deaths, 54 children and 41 neonates) were performed at the Maputo hospital, Mozambique. We compared the diagnoses obtained by the MIA blind to clinical data (MIAb), the MIA adding the clinical information (MIAc), and the CDA blind to clinical information (CDAb), with the results of the gold standard, the CDA with clinical data, by comparing the ICD-10 codes and the main diagnostic classes obtained with each evaluation strategy (MIAb, MIAc, CDAb, CDAc). The clinical data increased diagnostic coincidence to the MIAb with the gold standard in 30/264 (11%) cases and modified the CDAb diagnosis in 20/264 (8%) cases. The increase in concordance between MIAb and MIAc with the gold standard was significant in neonatal deaths (kappa increasing from 0.404 to 0.618, P=.0271), adult deaths (kappa increasing from 0.732 to 0.813, P=.0221) and maternal deaths (kappa increasing from 0.485 to 0.836, P<.0001). In conclusion, the use of clinical information increases the precision of MIA and CDA and may strengthen the performance of the MIA in resource-limited settings

Postmortem Interval and Diagnostic Performance of the Autopsy Methods

Postmortem studies, including the complete diagnostic autopsy (CDA) and the minimally invasive autopsy (MIA), an innovative approach to post-mortem sampling and cause of death investigation, are commonly performed within 24 hours after death because the quality of the tissues deteriorates over time. This short timeframe may hamper the feasibility of the procedure. In this study, we compared the diagnostic performance of the two postmortem procedures when carried out earlier and later than 24 hours after death, as well as the impact of increasing postmortem intervals (PMIs) on the results of the microbiological tests in a series of 282 coupled MIA/CDA procedures performed at the Maputo Central Hospital in Mozambique between 2013 and 2015. 214 procedures were conducted within 24 hours of death (early autopsies), and 68 after 24 hours of death (late autopsies). No significant differences were observed in the number of non-conclusive diagnoses (2/214 [1%] vs. 1/68 [1%] p = 0.5645 for the CDA; 27/214 [13%] vs. 5/68 [7%] p = 0.2332 for the MIA). However, increasing PMIs were associated with a raise in the number of bacteria identified (rate: 1.014 per hour [95%CI: 1.002-1.026]; p = 0.0228). This increase was mainly due to rising numbers of bacteria of the Enterobacteriaceae family and Pseudomonas genus strains. Thus, performing MIA or CDA more than 24 hours after death can still render reliable diagnostic results, not only for non-infectious conditions but also for many infectious diseases, although, the contribution of Enterobacteriaceae and Pseudomonas spp. as etiological agents of infections leading to death may be overestimated

The eyes follow the sound: Measuring speech perception with eye-tracking

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Dysmorphic syndrome in newborn with hypocholesterolemia

Introduction: There are various diseases caused by errors of the biosynthesis of cholesterol and Smith-Lemli-Opitz syndrome is the most frequent. Clinical Case: Infant admitted at 31 days of life with feeding difficulties since birth and failure to thrive. He presented dysmorphic craniofacial features and pos axial limb malformations, hypotonia, weak spontaneous movements and week reflexes. Investigation revealed hypocholesterolemia and an elevation of cholesterol precursors, which allowed the diagnosis of Smith-Lemli-Opitz syndrome, confirmed by molecular analysis. The administration of cholesterol resulted in weight gain. Discussion: The Smith-Lemli-Opitz syndrome is a multiple congenital malformation syndrome, of autosomal recessive transmission, resulting from an inborn error of cholesterol biosynthesis. It is caused by a defect in 7-dehydrocholesterol reductase, which decreases levels of cholesterol and elevates its precursors. Supplementation with cholesterol has been proven successful in the achievement of partial clinical improvements

SÍNDROME DE LEIGH: A PROPÓSITO DE UM CASO CLÍNICO COM MUTAÇÃO NO DNA MITOCONDRIAL

RESUMO Objetivo: A síndrome de Leigh é uma doença neurodegenerativa com incidência de 1:40.000 nados-vivos. Apresenta ampla heterogeneidade clínica, bioquímica e genética, mas com alterações neuropatorradiológicas homogêneas. Não existe tratamento específico, e o prognóstico é reservado. O objetivo deste estudo foi familiarizar os profissionais de saúde com a doença. Descrição do caso: Menina de 16 meses, com hipotonia axial e atraso do desenvolvimento psicomotor. Dos exames realizados: cariótipo, potenciais auditivos evocados e avaliação oftalmológica normais; presença de hiperlactacidemia e hipocitrulinemia. Após a realização de ressonância magnética cerebral sob anestesia, observou-se agravamento da hipotonia com necessidade de internação por episódios de cianose/apneia. O eletroencefalograma não mostrou atividade epileptiforme. A neuroimagem revelou hipersinal lenticular bilateral com lesão do putâmen e do globo pálido esquerdo. Encontrou-se a mutação 8993T>G (MT-ATP6) no DNA mitocondrial. Comentários: De 10 a 30% dos doentes com síndrome de Leigh apresentam mutações do DNA mitocondrial. A descompensação com agravamento neurológico após intervenção anestésica está descrita e, nesse caso, apoiou o diagnóstico. Importante alertar para casos semelhantes, com diminuição de exames invasivos para diagnóstico

Constrangimentos ao exercício da atividade da agricultura familiar e propostas de ação

info:eu-repo/semantics/publishedVersio

Ethyl acetate abatement on copper catalysts supported on ceria doped with rare earth oxides

Different lanthanide (Ln)-doped cerium oxides (Ce(0.5)Ln(0.5)O(1.75), where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N-2 adsorption at -196 degrees C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H-2. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO2 approximate to Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO2 and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 degrees C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. No particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen