Factors associated with anemia and vitamin A deficiency in Brazilian children under 5 years old: Brazilian National Survey on Child Nutrition (ENANI-2019).

Factors associated with anemia and vitamin A deficiency were investigated in 7,716 children 6-59 months of age studied in the Brazilian National Survey on Child Nutrition (ENANI-2019). We adopted a hierarchical approach based on a United Nations Children's Fund (UNICEF) theoretical model with three levels, stratifying by age (6-23; 24-59 months). Prevalence ratio (PR) and 95% confidence interval (95%CI) were estimated. Enabling determinants: a higher prevalence of anemia was observed in children 6-23 months whose mothers had ≤ 7 years of schooling (PR = 1.92; 95%CI: 1.10; 3.34), < 20 years old (PR = 2.47; 95%CI: 1.34; 4.56) or 20-30 years old (PR = 1.95; 95%CI: 1.11; 3.44), mixed-race (PR = 1.57; 95%CI: 1.06; 2.23); and in children 24-59 months in the North Region (PR = 3.11; 95%CI: 1.58; 6.13). A higher prevalence for vitamin A deficiency was observed in children 6-23 months from Central-West (PR = 2.32; 95%CI: 1.33; 4.05), and in children 24-59 months living in the North (PR = 1.96; 95%CI: 1.16; 3.30), South (PR = 3.07; 95%CI: 1.89; 5.01), and Central-West (PR = 1.91; 95%CI: 1.12; 3.25) and whose mothers were 20-34 years (PR = 1.62; 95%CI: 1.11; 2.35). Underlying determinants: the presence of more than one child < 5 years old in the household was associated with a higher prevalence of anemia (PR = 1.61; 95%CI: 1.15; 2.25) and vitamin A deficiency (PR = 1.82; 95%CI: 1.09; 3.05) in children 6-23 months. Immediate determinants: consumption of 1-2 groups of ultra-processed foods in children 24-59 months (PR = 0.44; 95%CI: 0.25; 0.81) and lack of breastfeeding in the day before in children 6-23 months (PR = 0.56; 95%CI: 0.36; 0.95) were associated with lower prevalence of anemia and vitamin A deficiency. Public policies focused on geographically and socially vulnerable groups are needed to promote equity.

Nickel Catalyzed Carbonylation/Carboxylation Sequence via Double CO2 Incorporation.

A carbonylation-carboxylation synthetic sequence, via double CO2 fixation, is described. The productive merger of a Ni-catalyzed cross-electrophile coupling manifold, with the use of AlCl3, triggered a cascade reaction with the formation of three consecutive C-C bonds in a single operation. This strategy traces an unprecedented synthetic route to ketones under Lewis acid assisted carbon dioxide valorization. Computational insights revealed a unique double function of AlCl3, and labeling (13CO2) experiments validate the genuine incorporation of CO2 in both functional groups.

Manganese(I)-Catalyzed Asymmetric Hydrophosphination of α,ß-Unsaturated Carbonyl Derivatives.

Here we report catalytic asymmetric hydrophosphination of α,ß-unsaturated carbonyl derivatives using a chiral Mn(I) complex as a catalyst. Through H-P bond activation, various phosphine-containing chiral products can be accessed via hydrophosphination of various ketone-, ester-, and carboxamide-based Michael acceptors.

Enantio- and Z-selective synthesis of functionalized alkenes bearing tertiary allylic stereogenic center.

Olefins are ubiquitous in biologically active molecules and frequently used as building blocks in chemical transformations. However, although many strategies exist for the synthesis of stereodefined E-olefines, their thermodynamically less stable Z counterparts are substantially more demanding, while access to those bearing an allylic stereocenter with an adjacent reactive functionality remains unsolved altogether. Even the classic Wittig reaction, arguably the most versatile and widely used approach to construct Z-alkenes, falls short for the synthesis of these particularly challenging yet highly useful structural motives. Here, we report a general methodology for Z-selective synthesis of functionalized chiral alkenes that establishes readily available alkene-derived phosphines as an alternative to alkylating reagents in Wittig olefination, thus offering previously unidentified retrosynthetic disconnections for the formation of functionalized disubstituted alkenes. We demonstrate the potential of this method by structural diversification of several bioactive molecules.

Catalytic Access to Chiral δ-Lactams via Nucleophilic Dearomatization of Pyridine Derivatives.

Nitrogen-bearing rings are common features in the molecular structures of modern drugs, with chiral δ-lactams being an important subclass due to their known pharmacological properties. Catalytic dearomatization of preactivated pyridinium ion derivatives emerged as a powerful method for the rapid construction of chiral N-heterocycles. However, direct catalytic dearomatization of simple pyridine derivatives are scarce and methodologies yielding chiral δ-lactams are yet to be developed. Herein, we describe an enantioselective C4-dearomatization of methoxypyridine derivatives for the preparation of functionalised enantioenriched δ-lactams using chiral copper catalysis. Experimental 13 C kinetic isotope effects and density functional theory calculations shed light on the reaction mechanism and the origin of enantioselectivity.

Factors associated with anemia and vitamin A deficiency in Brazilian children under 5 years old: Brazilian National Survey on Child Nutrition (ENANI-2019) / Fatores associados à anemia e deficiência de vitamina A em crianças brasileiras menores de cinco anos: Estudo Nacional de Alimentação e Nutrição Infantil (ENANI-2019) / Factores asociados con la anemia y la deficiencia de vitamina A en niños brasileños menores de cinco años: Estudio Nacional de Alimentación y Nutrición Infantil (ENANI-2019)

Abstract: Factors associated with anemia and vitamin A deficiency were investigated in 7,716 children 6-59 months of age studied in the Brazilian National Survey on Child Nutrition (ENANI-2019). We adopted a hierarchical approach based on a United Nations Children's Fund (UNICEF) theoretical model with three levels, stratifying by age (6-23; 24-59 months). Prevalence ratio (PR) and 95% confidence interval (95%CI) were estimated. Enabling determinants: a higher prevalence of anemia was observed in children 6-23 months whose mothers had ≤ 7 years of schooling (PR = 1.92; 95%CI: 1.10; 3.34), < 20 years old (PR = 2.47; 95%CI: 1.34; 4.56) or 20-30 years old (PR = 1.95; 95%CI: 1.11; 3.44), mixed-race (PR = 1.57; 95%CI: 1.06; 2.23); and in children 24-59 months in the North Region (PR = 3.11; 95%CI: 1.58; 6.13). A higher prevalence for vitamin A deficiency was observed in children 6-23 months from Central-West (PR = 2.32; 95%CI: 1.33; 4.05), and in children 24-59 months living in the North (PR = 1.96; 95%CI: 1.16; 3.30), South (PR = 3.07; 95%CI: 1.89; 5.01), and Central-West (PR = 1.91; 95%CI: 1.12; 3.25) and whose mothers were 20-34 years (PR = 1.62; 95%CI: 1.11; 2.35). Underlying determinants: the presence of more than one child < 5 years old in the household was associated with a higher prevalence of anemia (PR = 1.61; 95%CI: 1.15; 2.25) and vitamin A deficiency (PR = 1.82; 95%CI: 1.09; 3.05) in children 6-23 months. Immediate determinants: consumption of 1-2 groups of ultra-processed foods in children 24-59 months (PR = 0.44; 95%CI: 0.25; 0.81) and lack of breastfeeding in the day before in children 6-23 months (PR = 0.56; 95%CI: 0.36; 0.95) were associated with lower prevalence of anemia and vitamin A deficiency. Public policies focused on geographically and socially vulnerable groups are needed to promote equity.

Resumo: Fatores associados a anemia e deficiência de vitamina A foram investigados em 7.716 crianças de 6-59 meses de idade parte da Estudo Nacional de Alimentação e Nutrição Infantil (ENANI-2019). Adotamos uma abordagem hierárquica baseada em um modelo teórico do Fundo das Nações Unidas para a Infância (UNICEF) com três níveis estratificados por idade (6-23; 24-59 meses). Foram estimadas razões de prevalência (RP) e intervalos de 95% de confiança (IC95%). Determinantes habilitadores: observamos maior prevalência de anemia em crianças de 6-23 meses de idade cujas mães tinham ≤ 7 anos de escolaridade (RP = 1,92; IC95%: 1,10; 3,34), < 20 anos de idade (RP = 2,47; IC95%: 1,34; 4,56) ou 20-30 anos de idade (RP = 1,95; IC95%: 1,11; 3,44), cor parda (RP = 1,57; IC95%: 1,06; 2,23); e em crianças de 24-59 meses de idade na Região Norte (RP = 3,11; IC95%: 1,58; 6,13). Encontramos maior prevalência de deficiência de vitamina A em crianças de 6-23 meses de idade no Centro-oeste (RP = 2,32; IC95%: 1,33; 4,05) e em crianças de 24-59 meses de idade residentes nas regiões Norte (RP = 1,96; IC95%: 1,16; 3,30), Sul (RP = 3,07; IC95%: 1,89; 5,01) e Centro-oeste (RP = 1,91; IC95%: 1,12; 3,25) cujas mães tinham entre 20-34 anos de idade (RP = 1,62; IC95%: 1,11; 2,35). Determinantes subjacentes: a presença de mais de uma criança < 5 anos de idade no domicílio se associou a maior prevalência de anemia (RP = 1,61; IC95%: 1,15; 2,25) e deficiência de vitamina A (RP = 1,82; IC95%: 1,09; 3,05) em crianças de 6-23 meses de idade. Determinantes imediatos: o consumo de 1-2 grupos de alimentos ultraprocessados em crianças de 24-59 meses de idade (RP = 0,44; IC95%: 0,25; 0,81) e o não aleitamento materno no dia anterior em crianças de 6-23 meses de idade (RP = 0,56; IC95%: 0,36; 0,95) foram associados com a menor prevalência de anemia e deficiência de vitamina A. Políticas públicas focadas em grupos geográfica e socialmente vulneráveis são necessárias para promover equidade.

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Electrophilic Trapping of Semibenzenes.

In this work, we demonstrate how allylative dearomatization of benzyl chlorides can provide direct access to a variety of semibenzenes. These scaffolds behave as highly reactive nucleophiles in the presence of carbocations. In addition, semibenzenes are susceptible to intramolecular rearrangements rendering a broad scope of functionalized arenes. An analysis of this new reactivity is reported, as well as the rationale behind the observed intramolecular reorganizations.

Direct Synthesis of α-Aryl-α-Trifluoromethyl Alcohols via Nickel Catalyzed Cross-Electrophile Coupling.

A nickel-catalyzed reductive cross-electrophile coupling between the redox-active N-trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2-Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α-hydroxy-α-trifluoromethyl C-centered radical for the Csp2 -Csp3 bond forming process.

Connexin Expression in Pituitary Adenomas and the Effects of Overexpression of Connexin 43 in Pituitary Tumor Cell Lines.

Gap junction intercellular communication (GJIC) is considered a key mechanism in the regulation of tissue homeostasis. GJIC structures are organized in two transmembrane channels, with each channel formed by connexins (Cxs). GJIC and Cxs expression alterations are related to the process of tumorigenesis in different cell types. Pituitary neuroendocrine tumors (PitNETs) represent 15-20% of intracranial neoplasms, and usually display benign behavior. Nevertheless, some may have aggressive behavior, invading adjacent tissues, and featuring a high proliferation rate. We aimed to assess the expression and relevance of GJIC and Cxs proteins in PitNETs. We evaluated the mRNA expression levels of Cx26, 32, and 43, and the protein expression of Cx43 in a series of PitNETs. In addition, we overexpressed Cx43 in pituitary tumor cell lines. At the mRNA level, we observed variable expression of all the connexins in the tumor samples. Cx43 protein expression was absent in most of the pituitary tumor samples that were studied. Moreover, in vitro studies revealed that the overexpression of Cx43 decreases cell growth and induces apoptosis in pituitary tumor cell lines. Our results indicate that the downregulation of Cx43 protein might be involved in the tumorigenesis of most pituitary adenomas and have a potential therapeutic value for pituitary tumor therapy.

Violations to the principle of least motion: the shortest path is not always the fastest.

The reaction between two molecules is usually envisioned as following a least-motion path with both molecules travelling minimum distances to meet each other. However, the reaction path of lowest activation energy is not only determined by practicality but mainly by the orbital symmetry of the involved reactants and the efficiency of their mutual interaction. The term non-least-motion was born to design those reactions in which reactants follow, in their route to products, pathways longer than those intuitively expected. In this review we summarize the theoretical and experimental studies that describe and rationalize reactions following non-least-motion paths, starting with the dimerizations of carbenes and followed by additional processes of these and other reactive species (silylenes, carbynes) such as insertions into single bonds and additions to π-bonds. Other examples involving less reactive partners are also included.

Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation.

Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,ß-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.

Positive Youth Development and Wellbeing: Gender Differences.

The five C's of positive youth development (PYD) (competence, confidence, character, caring, and connection) have been associated with adaptive development among young people. Gender differences in young people's wellbeing and mental health have been studied and analyzed, but the investigation into their association with the five C's is still in its infancy. In the present study, we analyzed the influence of the five C's on the wellbeing, more specifically, anxiety, social alienation, general wellbeing, physical symptoms, and psychological symptoms, of Portuguese adolescents, by gender. Participants were 5th-12th grade students attending public schools in Lisbon, Portugal. The questionnaire was administered to 384 adolescents. The results indicated important gender differences in young people's wellbeing. The results revealed some differences between genders that should be considered in interventions that aim to promote the wellbeing of adolescents. On the other hand, confidence was positively associated with mental health and wellbeing for both boys and girls, skill should be promoted among young people, because it was competence that revealed the greatest association with wellbeing, among the variables analyzed.

Enantioselective Catalytic Dearomative Addition of Grignard Reagents to 4-Methoxypyridinium Ions.

We describe a general catalytic methodology for the enantioselective dearomative alkylation of pyridine derivatives with Grignard reagents, allowing direct access to nearly enantiopure chiral dihydro-4-pyridones with yields up to 98%. The methodology involves dearomatization of in situ-formed N-acylpyridinium salts, employing alkyl organomagnesium reagents as nucleophiles and a chiral copper (I) complex as the catalyst. Computational and mechanistic studies provide insights into the origin of the reactivity and enantioselectivity of the catalytic process.

National Survey on the importance of sleep in the quality of academic life and mental health of college students in Portugal.

The academic years are a period of vulnerability when considering sleep problems and mental health. Growing evidence suggests poor sleep patterns are related to impaired academic life and lower psychological well-being. The aim of this study was to explore the importance of sleep habits and report the associations of sleep problems with quality of academic life and different dimensions of mental health (e.g. worries, anxiety, self-regulation and resilience) in a large sample of college students. The HBSC/JUnP data base comprises a representative sample of 2991 college students (n=2203; 73.7% women), aged from 18 to 35 years old (22.43±3.83). Participants socio-demographic characteristics included sex and age. Besides, participants were inquired about sleep duration, characteristics of their sleep habits, questions about quality academic life, namely feeling bored in university, pressure from academic work and academic performance perception and mental health, namely worries, anxiety, self-regulation and resilience. Results showed most young people report an average value for sleep habits (M=4.41; SD=1.46) and that they sleep an average of 7 hours a night. More than half of the young people report either being affected by difficulty falling asleep, showing signs of sleep onset insomnia (67.7%). The conducted analyses indicated that the difficulty falling asleep (having insomnia) was associated with poor/reasonable academic performance perception, higher levels of concerns and anxiety, and lower levels of self-regulation and resilience, thus jeopardizing the mental health of college students. In turn, that characteristics of sleep was also associated with poor sleep habits. In conclusion, this study showed that poor sleep habits were associated with a worse level of academic performance perception and low levels of mental health among college students in Portugal. Universities offer enormous potential as settings to promote sleep-health programs since they can reach many young people who are future-oriented and willing to learn. There is then the need for academic researchers, teaching staff and health professionals working for college students health, to develop and test a wide array of sleep-promoting interventions (e.g., education classes, online programs, adjustment of class time), thus preventing negative secondary outcomes.

Nucleophilic Dearomatization of N-Heteroaromatics Enabled by Lewis Acids and Copper Catalysis.

Dearomative functionalization of heteroaromatics, a readily available chemical feedstock, is one of the most straightforward approaches for the synthesis of three-dimensional, chiral heterocyclic systems, important synthetic building blocks for both synthetic chemistry and drug discovery. Despite significant efforts, direct nucleophilic additions to heteroaromatics have remained challenging because of the low reactivity of aromatic substrates associated with the loss of aromaticity, as well the regio- and stereoselectivities of the reaction. Here we present a catalytic system that leads to unprecedented, high-yielding dearomative C-4 functionalization of quinolines with organometallics with nearly absolute regio- and stereoselectivities and with a catalyst turnover number (TON) as high as 1000. The synergistic action of the chiral copper catalyst, Lewis acid, and Grignard reagents allows us to overcome the energetic barrier of the dearomatization process and leads to chiral products with selectivities reaching 99% in most cases. Molecular modeling provides important insights into the speciation and the origin of the regio- and enantioselectivity of the catalytic process. The results reveal that the role of the Lewis acid is not only to activate the substrate toward a potential nucleophilic addition but also to subtly control the regiochemistry by preventing the C-2 addition from happening.

Lewis Acid Promoted Dearomatization of Naphthols.

Two-step dearomative functionalization of naphthols promoted by Lewis acids and copper(I) catalysis was developed. Initially, Lewis acid complexation inverted the electronic properties of the ring and established an equilibrium with the dearomatized counterpart. Subsequent trapping of the dearomatized intermediate with organometallics as well as organophosphines was demonstrated and provided the corresponding dearomatized products.

Long-Term Self-Regulation Moderates the Role of Internal Resources for Resilience in Positive Youth Development in Portugal.

Positive Youth Development (PYD) presents a strength-based conception of transition to adulthood that has been well-supported by literature to date. However, research is needed to integrate the pathways to PYD and the possible moderators. This study aimed to analyze the relationships between internal resources for resilience and PYD and to examine the moderating role of short-term and long-term self-regulation by gender. To reach this overall aim, a cross-sectional study was performed with a national sample of 2700 youths (73.3% girls; Mage = 21.3, SD = 2.79) from Portugal, who completed self-report measures. Regression-based moderation models were developed. Results indicated that greater presence of internal resources for resilience was related to higher PYD. Long-term self-regulation and gender moderated this relationship, such that a greater effect was observed in men with high levels of long-term self-regulation. These results highlight the need to integrate prevention and promotion paradigms to foster healthy development in youth, as well as the importance of taking self-regulation skills and gender into account in program design.

Small-molecule inhibition of aging-associated chromosomal instability delays cellular senescence.

Chromosomal instability (CIN) refers to the rate at which cells are unable to properly segregate whole chromosomes, leading to aneuploidy. Besides its prevalence in cancer cells and postulated implications in promoting tumorigenesis, studies in aneuploidy-prone mouse models uncovered an unanticipated link between CIN and aging. Using young to old-aged human dermal fibroblasts, we observed a dysfunction of the mitotic machinery arising with age that mildly perturbs chromosome segregation fidelity and contributes to the generation of fully senescent cells. Here, we investigated mitotic mechanisms that contribute to age-associated CIN. We found that elderly cells have an increased number of stable kinetochore-microtubule (k-MT) attachments and decreased efficiency in the correction of improper k-MT interactions. Chromosome mis-segregation rates in old-aged cells decreased upon both genetic and small-molecule enhancement of MT-depolymerizing kinesin-13 activity. Notably, restored chromosome segregation accuracy inhibited the phenotypes of cellular senescence. Therefore, we provide mechanistic insight into age-associated CIN and disclose a strategy for the use of a small-molecule to inhibit age-associated CIN and to delay the cellular hallmarks of aging.

Synthesis and Functionalization of Allenes by Direct Pd-Catalyzed Organolithium Cross-Coupling.

A palladium-catalyzed cross-coupling between in situ generated allenyl/propargyl-lithium species and aryl bromides to yield highly functionalized allenes is reported. The direct and selective formation of allenic products preventing the corresponding isomeric propargylic product is accomplished by the choice of SPhos or XPhos based Pd catalysts. The methodology avoids the prior transmetalation to other transition metals or reverse approaches that required prefunctionalization of substrates with leaving groups, resulting in a fast and efficient approach for the synthesis of tri- and tetrasubstituted allenes. Experimental and theoretical studies on the mechanism show catalyst control of selectivity in this allene formation.

Synthesis of Spirobicyclic Pyrazoles by Intramolecular Dipolar Cycloadditions/[1s, 5s] Sigmatropic Rearrangements.

The formation of fused pyrazoles via intramolecular 1,3-dipolar cycloadditions of diazo intermediates with pendant alkynes is described. A subsequent thermal [1s, 5s] sigmatropic shift of these pyrazole systems resulted in a ring contraction, forming spirocyclic pyrazoles. The limitations of this rearrangement were explored by changing the substituents on the nonmigrating aromatic ring and by using substrates lacking an aromatic linkage to the propargyl group.