An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter

A new persistent organic free radical has been synthetized with Br atoms occupying the ortho‐ and para‐positions of a trityl core. After the isolation of its two propeller‐like atropisomers, Plus (P) and minus (M), their absolute configurations were assigned by a combination of theoretical and experimental data. Remarkably, no hints of racemization were observed up to 60 °C for more than two hours, due to the higher steric hindrance imposed by the bulky Br atoms. Therefore, when compared to its chlorinated homologue (t1/2=18 s at 60 °C), an outstanding stability against racemization was achieved. A circularly polarized luminescence (CPL) response of both enantiomers was detected. This free radical shows a satisfactory luminescent dissymmetry factor (|glum(592 nm)|≈0.7×10−3) despite its pure organic nature and low luminescence quantum yield (LQY). Improved organic magnetic CPL emitters derived from the reported structure can be envisaged thanks to the wide possibilities that Br atoms at para‐positions offer for further functionalization.The authors are grateful for the financial support received from: MOTHER project (MAT2016-80826-R) granted by the DGI (Spain), GenCat (2017-SGR-918) financed by DGR (Catalunya) and the Spanish Ministry of Economy and Competitiveness (PGC2018-095808-B-I00 and PGC2018-101181-B-I00 projects) and through the “Severo Ochoa” Programme for Centres of Excellence in R&D (SEV-2015-0496) and through the “Proyecto Interdisciplinar de Frontera“, FIP-2018 HECTIC-PTM. We acknowledge the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (ERC-2015-STG-677023). This study has been also supported by the Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), an initiative funded by the VI National R&D&I Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. P. M. B. gratefully acknowledges financial support from the Juan de la Cierva-Formación 2015 programme (FJCI-2015-23577) supported by MINECO and, together with J.V, A. G. C. also thanks RyC-2013-12943 contract from MINECO. We also thankthe Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona, for allocating instrument time to this project

Early-onset Alzheimer's disease shows a distinct neuropsychological profile and more aggressive trajectories of cognitive decline than late-onset

Early- and late-onset Alzheimer's disease (EOAD and LOAD) share the same neuropathological traits but show distinct cognitive features. We aimed to explore baseline and longitudinal outcomes of global and domain-specific cognitive function in a well characterized cohort of patients with a biomarker-based diagnosis.In this retrospective cohort study, 195 participants were included and classified according to their age, clinical status, and CSF AD biomarker profile: 89 EOAD, 37 LOAD, 46 young healthy controls (age???65?years), and 23 old healthy controls (>65?years). All subjects underwent clinical and neuropsychological assessment, neuroimaging, APOE genotyping and lumbar puncture.We found distinct neuropsychological profiles between EOAD and LOAD at the time of diagnosis. Both groups showed similar performances on memory and language domains, but the EOAD patients displayed worsened deficits in visual perception, praxis, and executive tasks (p?<?0.05). Longitudinally, cognitive decline in EOAD was more pronounced than LOAD in the global outcomes at the expense of these non-amnestic domains. We found that years of education significantly influenced the decline in most of the neuropsychological tests. Besides, the APOE ?4 status showed a significant effect on the decline of memory-related tasks within the EOAD cohort (p?<?0.05).Age of onset is a main factor shaping the cognitive trajectories in AD patients, with younger age driving to a steeper decline of the non-memory domains. Years of education are related to a transversal decline in all cognitive domains and APOE ?4 status to a specific decline in memory performance in EOAD.© 2022 The Authors. Annals of Clinical and Translational Neurology published by Wiley Periodicals LLC on behalf of American Neurological Association

ASPM and microcephalin expression in epithelial ovarian cancer correlates with tumour grade and survival

BACKGROUND: The clinico-pathological and molecular heterogeneity of epithelial ovarian cancer (EOC) complicates its early diagnosis and successful treatment. Highly aneuploid tumours and the presence of ascitic fluids are hallmarks of EOC. Two microcephalyassociated proteins, abnormal spindle-like microcephaly-associated protein (ASPM) and microcephalin, are involved in mitosis and DNA damage repair. Their expression is deregulated at the RNA level in EOC. Here, ASPM and microcephalin protein expression in primary cultures established from the ascites of patients with EOC was determined and correlated with clinical data to assess their suitability as biomarkers. METHODS: Five established ovarian cancer cell lines, cells derived from two benign ovarian ascites samples and 40 primary cultures of EOC derived from ovarian ascites samples were analysed by protein slot blotting and/or immunofluorescence to determine ASPM and microcephalin protein levels and their cellular localisation. Results were correlated with clinico-pathological data. RESULTS: A statistically significant correlation was identified for ASPM localisation and tumour grade, with high levels of cytoplasmic ASPM correlating with grade 1 tumours. Conversely, cytoplasmic microcephalin was only identified in high-grade tumours. Furthermore, low levels of nuclear microcephalin correlated with reduced patient survival. CONCLUSION: Our results suggest that ASPM and microcephalin have the potential to be biomarkers in ovarian cance

Energy Sorghum : An alternative energy crop A Handbook

Increasing world market prices for fossil fuels, driven by limited reserves, growing demand and instability in producing regions, now render renewable fuels economical. Such fuels are also a pathway to reducing greenhouse gas (GHG) emissions and mitigating climate change. The transport sector which is almost totally dependent on fossil fuels, particularly for powering personal vehicles and trucks, is the most concerned sector. Biofuels, defined as solid, liquid or gas fuels derived from biomass, are today the only direct substitute for fossil fuels on a significant scale particularly in transport sector. Biofuels are considered environmentally friendly because the CO2 emissions they produce during combustion is balanced by the CO2 absorbed by the plants growth. To be a viable substitute for fossil fuels, an alternative fuel should not only have superior environmental benefits over the fossil fuels it substitutes, be economically competitive with it, and be available in sufficient quantities to make meaningful impact on energy demand, but it should also provide a net energy gain over the energy invested to produce it and have minimal effect on food security... {This handbook was elaborated in the framework of the SWEETFUEL project (grant agreement number 227422), supported by the European Commission

The possible role of local air pollution in climate change in West Africa

The climate of West Africa is characterized by a sensitive monsoon system that is associated with marked natural precipitation variability. This region has been and is projected to be subject to substantial global and regional-scale changes including greenhouse-gas-induced warming and sea-level rise, land-use and land-cover change, and substantial biomass burning. We argue that more attention should be paid to rapidly increasing air pollution over the explosively growing cities of West Africa, as experiences from other regions suggest that this can alter regional climate through the influences of aerosols on clouds and radiation, and will also affect human health and food security. We need better observations and models to quantify the magnitude and characteristics of these impacts

Social times, reproduction and social inequality at work : contrasts and comparative perspectives between countries

Production of INCASI Project H2020-MSCA-RISE-2015 GA 691004If the focus is placed specifically on the problem of work and family, the daily life of people and their use of time are a main problem. This time is expressed in both freely available time, which is related to activities, and time of the productive and reproductive sphere. This chapter considers work in a broad sense and takes into account the sexual division of labour. Specifically, this chapter will explore transformations in time use and social inequality in unpaid work. For this purpose, a comparative analysis of time-use surveys will be used, analysing the time spent, and the time dedicated to household chores in Chile, Argentina, Uruguay and Spain. From an analytical viewpoint, the analysis will place social reproduction at the centre of the socio-economic system, showing that the economic crisis has affected women and men differently, and that in both Europe and Latin America the family pattern is being replaced by a dominant family model of a male provider and a double presence of women. The large-scale incorporation of women into the labour market has emphasised the role that women assume in the domestic sphere perpetuating gender segregation in employment and in domestic and care work

An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter

A new persistent organic free radical has been synthetized with Br atoms occupying the ortho‐ and para‐positions of a trityl core. After the isolation of its two propeller‐like atropisomers, Plus (P) and minus (M), their absolute configurations were assigned by a combination of theoretical and experimental data. Remarkably, no hints of racemization were observed up to 60 °C for more than two hours, due to the higher steric hindrance imposed by the bulky Br atoms. Therefore, when compared to its chlorinated homologue (t1/2=18 s at 60 °C), an outstanding stability against racemization was achieved. A circularly polarized luminescence (CPL) response of both enantiomers was detected. This free radical shows a satisfactory luminescent dissymmetry factor (|glum(592 nm)|≈0.7×10−3) despite its pure organic nature and low luminescence quantum yield (LQY). Improved organic magnetic CPL emitters derived from the reported structure can be envisaged thanks to the wide possibilities that Br atoms at para‐positions offer for further functionalization.The authors are grateful for the financial support received from: MOTHER (MAT2016‐80826‐R) and FANCY (CTQ2016‐80030‐R) projects, granted by the DGI (Spain), GenCat (2017‐SGR‐918) financed by DGR (Catalunya) and the Spanish Ministry of Economy and Competitiveness (PGC2018‐095808‐B‐I00 and PGC2018‐101181‐B‐I00 projects) and through the „Severo Ochoa“ Programme for Centres of Excellence in R&D (SEV‐2015‐0496) and through the „Proyecto Interdisciplinar de Frontera“, FIP‐2018 HECTIC‐PTM. We acknowledge the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (ERC‐2015‐STG‐677023). This study has been also supported by the Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER‐BBN), an initiative funded by the VI National R&D&I Plan 2008–2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. P.M.B. gratefully acknowledges financial support from the Juan de la Cierva‐Formación 2015 programme (FJCI‐2015–23577) supported by MINECO and, together with J.V, A.G.C. is grateful for a RyC‐2013–12943 contract from MINECO. We also thank the Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona, for allocating instrument time to this project.Peer reviewe