Total Synthesis of (Nor)illudalane Sesquiterpenes Based on a C(sp3)-H Activation Strategy

Three (nor)illudalane sesquiterpenes were synthesized from a common intermediate in racemic and enantioenriched forms using Pd0-catalyzed C(sp3)-H arylation as a key step. The configuration of the isolated, highly symmetric quaternary stereocenter of the target molecules was controlled through a matched combination of chiral substrate and catalyst. Moreover, the recently developed Ir-catalyzed C-H borylation/Cu-catalyzed methylation method was employed to install the methyl group on the benzene ring. This strategy allowed the efficient synthesis of both racemic and (S)-configured puraquinonic acid, deliquinone, and russujaponol F

Divergent Enantioselective Synthesis of (Nor)illudalane Sesquiterpenes via Pd-0-Catalyzed Asymmetric C(sp(3))-H Activation

A divergent enantioselective synthesis of (nor)-illudalane sesquiterpenes was designed by using a Pd-0-catalyzed asymmetric C(sp(3))-H arylation as a key step to control the isolated, highly symmetric quaternary stereocenter of the target molecules. A matched combination of chiral substrate and catalyst proved optimal to reach good levels of stereoselectivity. This approach enabled the synthesis of three (nor)illudalanes, including (S)-deliquinone and (S)-russujaponol F, which are synthesized for the first time in enantioenriched form

How the metabolic phenotype in adulthood is affected by long-lasting immunological trajectories since adolescence

A close relationship between immune and metabolic systems has been perceived in the recent past. We aimed to assess whether the immunological trajectories of circulating white blood cells (WBC) started in adolescence, affects the metabolic phenotype in adulthood. We used data from 1183 participants of the population-based EPITeen cohort, evaluated at 13, 17, 21, 24 and 27 years of age. The Immunological trajectories from 13 to 27 years old were identified by mixed-effects models, being their association with metabolic features at 27 years old measured by logistic regression. The Higher Inflammatory Activation trajectory (HIA trajectory) had the highest percentage of individuals with metabolic syndrome, while Lowest Levels of WBC trajectory (LLWBC trajectory) showed the lowest percentage. Participants with HIA trajectory had significantly higher triglycerides, waist circumference, serum uric acid and BMI. After adjustment for sex and sports practice and hs-CRP, the odds of having one or more metabolic features in adulthood was significantly lower in LLWBC trajectory. Individuals with immunological trajectories of WBC linked with a pattern of higher immune activation showed a less favorable metabolic profile, while those with the lowest levels of WBC were less likely to have metabolic risk factors in adulthood. © 2022, The Author(s).This study was financed by national funds through the Foundation for Science and Technology (Portuguese public agency that supports science, technology and innovation, in all scientific domains, under responsibility of the Ministry of Science, Technology and Higher Education), under the Project UIDB/04750/2020 and under the scientific Project PTDC/DTP-EPI/6506/2014 and the doctoral studentship PD/BD/149264/2019 (VC)

Immunological Trajectories of White Blood Cells from Adolescence to Adulthood: Description and Determinants

Background: The immune system gradually matures early in life in the face of internal and external stimuli. Whether the immune responses are lasting and stable during the course of life is still unclear. Methods: As part of the EPITeen cohort, 1183 adolescents were prospectively evaluated at the ages of 13, 17, 21, 24 and 27. Sociodemographic, behavioral and clinical data were collected by self- and face-to-face-administered questionnaires, along with a physical examination comprising anthropometric measurements and blood sample collections. Mixed-effects models were used to identify individual trajectories of white blood cells (WBC) and finite Gaussian mixture models were used to identify the clusters of individual trajectories. Results: Participants were allocated into six clusters based on the individual trajectories of WBC distribution. Higher Inflammatory Activation Cluster (11.4%) had the highest total WBC count and neutrophils percentage, as well as the lowest percentage of lymphocytes. These participants had significantly higher odds of being overweight [OR = 2.44, 95%CI:1.51-3.92]. Lowest Levels of WBC Cluster (24.1%) had the lowest total WBC count, being characterized by a higher participation on sports [OR = 1.54, 95%CI:1.12-2.13]. Highest Proportion of Eosinophils Cluster (20.1%) had the highest eosinophils percentage and the highest likelihood of having been diagnosed with a chronic disease [OR = 2.11, 95%CI:1.43-3.13], namely "asthma or allergies" [OR = 14.0 (1.73, 112.2]. Lowest Proportion of Eosinophils Cluster (29.1%) had the lowest percentage of eosinophils and basophils, as well as the highest lymphocyte proportion. Participants in the Undefined Cluster (13.8%) showed the highest percentage of monocytes and basophils and were also characterized by significant lower odds of having parents with 7-9 years of schooling [OR = 0.56, (0.32, 0.99]. Conclusions: In this study we identified distinct immunological trajectories of WBC from adolescence to adulthood that were associated with social, clinical and behavioral determinants. These results suggest that these immunological trajectories are defined early in life, being dependent on the exposures.This study was funded by FEDER through the Operational Programme Competitiveness and Internationalization and by national funding from the Foundation for Science and Technology—FCT (Portuguese Ministry of Science, Technology and Higher Education) (POCI-01-0145-FEDER-016829), under Unidade de Investigação em Epidemiologia—Instituto de Saúde Pública da Universidade do Porto (EPIUnit) (POCI-01-0145-FEDER-006862; Ref. info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UID/DTP/04750/2013/PT); and the individual PhD Grant to VC (PD/BD/149264/2019), co-funded by the FCT and the POPH/FSE Program

Association of Serum 25-Hydroxyvitamin D Concentration with Pulmonary Function in Young Adults

The role of vitamin D on pulmonary function is unclear and is mostly studied in patients, smokers and elderly people. The aim of this paper was to evaluate the association between serum 25-hydroxyvitamin D [25(OH)D] concentration and pulmonary function in young adults. Cross-sectional analysis of 499 individuals that were evaluated at 21 years of age as part of the population-based cohort Epidemiological Health Investigation of Teenagers in Porto (EPITeen). Serum 25(OH)D was categorized according to the Institute of Medicine. Pulmonary function was evaluated using spirometry. Linear regression models were used to estimate the regression coefficients (beta) and its 95% confidence intervals (95% CI), and were adjusted for confounders. Education, smoking, body mass index, and season of evaluation were determinants of serum 25(OH)D concentration. Prevalence of serum 25(OH)D concentration = 50 nmol/L, PEF was significantly lower for those with a concentration of 30 to < 50 nmol/L (beta = -0.576; 95% CI: -0.943, -0.210), and for those with a concentration of <30 nmol/L (beta = - 0.650; 95% CI: -1.155, -0.146). Although only PEF attained statistical significance, the consistent results with the other parameters support the role of serum 25(OH)D to promote better pulmonary function in young adults.This study was funded by FEDER through the Operational Programme Competitiveness and Internationalization and national funding from the Foundation for Science and Technology-FCT (Portuguese Ministry of Science, Technology and Higher Education) (POCI-01-0145-FEDER-016829), under the project Uma abordagem longitudinal a obesidade metabolicamente saudavel: da inflamacao ao perfil de risco cardiovascular (Ref. FCT PTDC/DTP-EPI/6506/2014) and the Unidade de Investigacao em Epidemiologia -Instituto de Saude Publica da Universidade do Porto (EPIUnit) (POCI-01-0145-FEDER-006862; Ref. UID/DTP/04750/2013); and the PhD Grant PD/BD/105824/2014 (Maria Cabral), co-funded by the FCT and the POPH/FSE Program

Vitamin D - from the pro-hormone to the biological actions

A vitamina D (calciferol) é uma pró-hormona lipossolúvel que apresenta duas formas principais - vitamina D2 (ergocalciferol) e vitamina D3 (colecalciferol). A vitamina D2 é obtida via irradiação ultravioleta B (UVB) do ergosterol, um esterol dos fungos, e a vitamina D3 é sintetizada na pele humana/animal, após exposição do 7-desidrocolesterol à radiação UVB. Ambas as formas são produzidas comercialmente e encontradas em suplementos e alimentos fortificados. Quer provenham da síntese cutânea (D3), quer da dieta (D2 e D3), ambas as vitaminas precisam de ser ativadas, o que requer duas reações de hidroxilação, uma mediada pela 25-hidroxilase e outra mediada pela 1α-hidroxilase. Assim, quer a vitamina D2 quer a D3 originam o calcitriol. Este metabolito ativo é responsável por ações biológicas caracterizadas como genómicas, mediadas pelos efeitos transcricionais do recetor de vitamina D (VDR) nos núcleos das células-alvo, e não genómicas, mediadas pelas vias rápidas de transdução de sinal induzidas pelo VDR na membrana celular e/ou citoplasma. Além das ações endócrinas do calcitriol (regulação de cálcio e fósforo, com interações ao nível dos rins, ossos, glândulas paratiroides, e jejuno), a presença ubíqua de VDR no organismo contribui para as ações autócrinas e parácrinas do calcitriol, tal como a inibição da proliferação celular, promoção da diferenciação celular (incluindo a diferenciação de queratinócitos), apoptose e regulação da resposta imune. Além disso, o calcitriol está envolvido na ação preventiva e terapêutica do cancro, nas doenças autoimunes (como a diabetes tipo 1), doenças cardiovasculares e infeções.This study was funded by FEDER through the Operational Programme Competitiveness and Internationalization and national funding from the Foundation for Science and Technology – FCT (Portuguese Ministry of Science, Technology and Higher Education) (POCI-01-0145-FEDER-016829), under the Unidade de Investigação em Epidemiologia- Instituto de Saúde Pública da Universidade do Porto (EPIUnit) (POCI-01-0145-FEDER-006862; Ref. UID/DTP/04750/2013; and the PhD Grant PD/BD/149264/2019 (Vanda Craveiro), co-funded by the FCT and the POPH/FSE Program

Ciclo de vida y dinámica poblacional de la enigmática tanaide Chondrochelia dubia (Tanaidacea: Leptocheliidae) en un lecho de algas tropicales

The present study describes the population dynamics and life history parameters of the enigmatic tanaid Chondrochelia dubia collected in Paiva Beach, tropical coast of Brazil. The region was impacted by a large, unexpected oil spill from August to October 2019. Samples were taken monthly between July 2019 and July 2020 in beds of the red seaweed Jania capillacea. The abundance of individuals was negatively correlated with monthly rainfall, with higher abundances in drier months. There was an unexpected significant drop in abundance in September, possibly caused by contact with the crude oil, but the population recovered fully within two months. The parameters of the von Bertallanfy growth equation, calculated for the first time for the species, were Linf=5.26 mm; k=3.36 year–1; t0=0.0. Compared with other studies, the specimens are very small (2.04 ± 0.95 mm in length), females reach sexual maturity very early (L50=2.3 mm), and natural mortality is high (Z=M=5.77 year–1), indicating an opportunistic life strategy. This study reinforces the bioindication potential of C. dubia and the use of bootstrapped length-based methods to estimate key population parameters in small marine invertebrates.El presente estudio describió la dinámica poblacional y los parámetros del ciclo de vida del enigmático tanaidáceo Chondrochelia dubia recolectado en la playa de Paiva, costa tropical de Brasil. La región se vio afectada por un gran derrame de petróleo inesperado de agosto a octubre de 2019. Se tomaron muestras mensualmente entre julio de 2019 y julio de 2020 en lechos de algas rojas Jania capillacea. La abundancia de individuos se correlacionó negativamente con la precipitación mensual, con mayor abundancia en los meses más secos. Hubo una inesperada caída significativa de la abundancia en septiembre, posiblemente causada por el contacto con el petróleo crudo, sin embargo, la población se recuperó por completo en dos meses. Los parámetros de la ecuación de crecimiento de von Bertallanfy, calculados por primera vez para la especie, fueron: Linf=5.26 mm; k=3.36 año–1; t0=0,0. En comparación con otros estudios, los ejemplares son muy pequeños (2.04 ± 0.95 mm de longitud), las hembras alcanzan la madurez sexual muy temprano (L50=2.3 mm), y la mortalidad natural es relativamente alta (Z=M=5.77 año–1), lo que indica una estrategia de vida oportunista. Este estudio refuerza el potencial de bioindicación de C. dubia y el uso de métodos bootstrap basados en la longitud para estimar parámetros de población clave en pequeños invertebrados marinos

Visitantes florais de dendê, caiaué e híbrido interespecífico: abundância, diversidade e interações.

Objetivou-se estudar a diversidade, abundância e a relação entre os visitantes florais de dendê, caiaué e do HIE

Avaliação da resistência de genótipos de milho, sorgo e milheto a Meloidogyne javanica e M. incognita raca 3.

O uso de espécies cultivadas resistentes aos nematóides formadores de galhas, em sistemas de rotação de culturas, mantém a população dos nematóides em níveis baixos, diminuindo as perdas e possibilitando o plantio de espécies mais susceptíveis. No presente trabalho avaliou-se a resistência de genótipos de milho, sorgo e milheto aos nematóides de galhas Meloidogyne javanica e M. incognita raça 3. Os ensaios foram conduzidos em casa de vegetação e os genótipos semeados em vasos plásticos contendo 2 litros de substrato esterilizado (três partes de areia e uma de solo), e inoculados com 5.000 ovos de nematóide por vaso, dispostos em delineamento inteiramente casualizado com oito repetições. Plantas de tomateiro foram utilizadas para confirmar a viabilidade do inóculo. A avaliação da reprodução dos nematóides foi feita 60 dias após a inoculação, através da contagem do número de ovos por sistema radicular das plantas de cada genótipo, calculando-se o Fator de Reprodução (FR=Pf/Pi, sendo Pf a população final de ovos e larvas de nematóide e Pi a população inicial). De acordo com os resultados, todos os genótipos de milho, sorgo e milheto comportaram-se como resistentes à reprodução de M. javanica; quanto à M. incognita raça 3, mostraram maior nível de resistência os genótipos de milho, CMS 100 02 2, HS 723x724, 97 HT 14 A, BRS 3123, BRS 2114, CMS 14 B, CMS 2000 17 A, CMS 99 14 C, 52 HT03-QPM, HS 111764040, e todos os genótipos de sorgo e de milheto. Os genótipos resistentes comerciais são indicados para uso em rotação em áreas infestadas por esses nematóides