Organocatalytic Michael Addition of Unactivated α-Branched Nitroalkanes to Afford Optically Active Tertiary Nitrocompounds.

The direct, asymmetric conjugate addition of unactivated α-branched nitroalkanes is developed based on the combined use of chiral amine/ureidoaminal bifunctional catalysts and a tunable acrylate template to provide tertiary nitrocompounds in 55-80% isolated yields and high enantioselectivity (e.r. up to 96:4). Elaboration of the ketol moiety in thus obtained adducts allows a fast entry to not only carboxylic and aldehyde derivatives but also nitrile compounds and enantioenriched 5,5-disubstituted γ-lactams.

Tetrahedraphene: A Csp3 -centered 3D Molecular Nanographene Showing Aggregation-Induced Emission.

The bottom-up synthesis of 3D tetrakis(hexa-peri-hexabenzocoronenyl)methane, "tetrahedraphene", is reported. This molecular nanographene constituted by four hexa-peri-hexabenzocoronene (HBC) units attached to a central sp3 carbon atom, shows a highly symmetric arrangement of the HBC units disposed in the apex of a tetrahedron. The X-ray crystal structure reveals a tetrahedral symmetry of the molecule and the packing in the crystal is achieved mostly by CH⋅⋅⋅π interactions since the interstitial solvent molecules prevent the π⋅⋅⋅π interactions. In solution, tetrahedraphene shows the same electrochemical and photophysical properties as the hexa-t Bu-substituted HBC (t Bu-HBC) molecule. However, upon water addition, it undergoes a fluorescence change in solution and in the precipitated solid, showing an aggregation induced emission (AIE) process, probably derived from the restriction in the rotation and/or vibration of the HBCs. Time-Dependent Density Functional Theory (TDDFT) calculations reveal that upon aggregation, the high energy region of the emission band decreases in intensity, whereas the intensity of the red edge emission signal increases and presents a smoother decay, compared to the non-aggregated molecule. All in all, the excellent correlation between our simulations and the experimental findings allows explaining the colour change observed in the different solutions upon increasing the water fraction.

Development of an α'-hydroxy enone for the aminocatalytic asymmetric formal conjugate addition of aldehydes to acrylates, vinyl ketones and acrolein.

Aminocatalytic asymmetric conjugate addition of aldehydes to Michael acceptors is a well established C-C bond forming methodology. However, various acrylic-type acceptors, including acrylic acid derivatives and acrolein, remain reluctant. Here we demonstrate that the internal H-bonding self-activation in α'-hydroxy enones allows them to react smoothly with enolizable aldehydes using commercially available aminocatalysts to afford adducts in good yields and high enantioselectivity. Straightforward conversion of the ketol moiety of these adducts into aldehyde, ketone and carboxylic acid functionalities offers an indirect, unified entry to products derived from acrolein, alkyl-vinyl ketones and acrylates, respectively.

Helical Bilayer Nanographenes: Impact of the Helicene Length on the Structural, Electrochemical, Photophysical, and Chiroptical Properties.

Helical bilayer nanographenes (HBNGs) are chiral π-extended aromatic compounds consisting of two π-π stacked hexabenzocoronenes (HBCs) joined by a helicene, thus resembling van der Waals layered 2D materials. Herein, we compare [9]HBNG, [10]HBNG, and [11]HBNG helical bilayers endowed with [9], [10], and [11]helicenes embedded in their structure, respectively. Interestingly, the helicene length defines the overlapping degree between the two HBCs (number of benzene rings involved in π-π interactions between the two layers), being 26, 14, and 10 benzene rings, respectively, according to the X-ray analysis. Unexpectedly, the electrochemical study shows that the lesser π-extended system [9]HBNG shows the strongest electron donor character, in part by interlayer exchange resonance, and more red-shifted values of emission. Furthermore, [9]HBNG also shows exceptional chiroptical properties with the biggest values of gabs and glum (3.6 × 10-2) when compared to [10]HBNG and [11]HBNG owing to the fine alignment in the configuration of [9]HBNG between its electric and magnetic dipole transition moments. Furthermore, spectroelectrochemical studies as well as the fluorescence spectroscopy support the aforementioned experimental findings, thus confirming the strong impact of the helicene length on the properties of this new family of bilayer nanographenes.

Curved Nanographenes: Multiple Emission, Thermally Activated Delayed Fluorescence, and Non-Radiative Decay.

The intriguing and rich photophysical properties of three curved nanographenes (CNG 6, 7, and 8) are investigated by time-resolved and temperature-dependent photoluminescence (PL) spectroscopy. CNG 7 and 8 exhibit dual fluorescence, as well as dual phosphorescence at low temperature in the main PL bands. In addition, hot bands are detected in fluorescence as well as phosphorescence, and, in the narrow temperature range of 100-140 K, thermally activated delayed fluorescence (TADF) with lifetimes on the millisecond time-scale is observed. These findings are rationalized by quantum-chemical simulations, which predict a single minimum of the S1 potential of CNG 6, but two S1 minima for CNG 7 and CNG 8, with considerable geometric reorganization between them, in agreement with the experimental findings. Additionally, a higher-lying S2 minimum close to S1 is optimized for the three CNG, from where emission is also possible due to thermal activation and, hence, non-Kasha behavior. The presence of higher-lying dark triplet states close to the S1 minima provides mechanistic evidence for the TADF phenomena observed. Non-radiative decay of the T1 state appears to be thermally activated with activation energies of roughly 100 meV and leads to disappearance of phosphorescence and TADF at T > 140 K.

Electronic Control of the Scholl Reaction: Selective Synthesis of Spiro vs Helical Nanographenes.

Scholl oxidation has become an essential reaction in the bottom-up synthesis of molecular nanographenes. Herein, we describe a Scholl reaction controlled by the electronic effects on the starting substrate (1 a, b). Anthracene-based polyphenylenes lead to spironanographenes under Scholl conditions. In contrast, an electron-deficient anthracene substrate affords a helically arranged molecular nanographene formed by two orthogonal dibenzo[fg,ij]phenanthro-[9,10,1,2,3-pqrst]pentaphene (DBPP) moieties linked through an octafluoroanthracene core. Density Functional Theory (DFT) calculations predict that electronic effects control either the first formation of spirocycles and subsequent Scholl reaction to form spironanographene 2, or the expected dehydrogenation reaction leading solely to the helical nanographene 3. The crystal structures of four of the new spiro compounds (syn 2, syn 9, anti 9 and syn 10) were solved by single crystal X-ray diffraction. The photophysical properties of the new molecular nanographene 3 reveal a remarkable dual fluorescent emission.

Sense of Agency, Affectivity and Social-Ecological Degradation: An Enactive and Phenomenological Approach.

In the last few years, there has been an interest in understanding the impact of environmental change and degradation on people's affective life. This issue has become particularly pressing for populations whose form of life is heavily dependent on ecosystem services and functions and whose opportunities for adaptation are limited. Based on our work with farmers from the Xochimilco urban wetland in the southwest of Mexico City, we begin to draw a theoretical approach to address and explain how environmental degradation impacts people's affective life and sense of agency. Farmers who were part of our project referred to a sense of despair and helplessness toward the loss of the ecosystem and their traditional farming-based form of life. From the perspective of phenomenology, enactivism and ecological psychology, we argue that the loss of this form of life in the area is related to the degradation of socio-ecological systems, limiting the opportunities for people to relate meaningfully to others and the environment. We posit that losing meaningful interaction with the environment generates a feeling of loss of control while leading farmers to feel frustrated, anxious and stressed. Such affective conditions have a direct impact on their sense of agency. In terms of adaptation, the negative interaction between degradation, affective states and a diminished sense of agency can create a downward spiral of vulnerability, including political vulnerability.

Body Composition and Nutrients Dietary Intake Changes during COVID-19 Lockdown in Spanish Healthy Postmenopausal Women.

(1) Background: During the COVID-19 lockdown, high rates of physical inactivity and dietary imbalances were reported in both adults and adolescents. Physical separation and isolation not only have a significant impact on the performance of physical activity but also affect people's lives, particularly their dietary habits. In the present study, we aimed to examine whether or not bioelectrical impedance-derived body composition parameters and dietary habits were affected during the pandemic-associated lockdown in postmenopausal Spanish women. (2) Methods: Sixty-six women participated in the study (58.7 ± 5.4 years) before (between July−October 2019) and after (August−October 2020) the lockdown, which occurred as a consequence of the COVID-19 pandemic in Spain. Body composition parameters were measured by bioelectrical impedance analysis while dietary intake of proteins, fat, carbohydrates, and energy was measured by a food frequency questionnaire. (3) Results Regarding body composition, no differences were observed in fat mass in % (mean increase 0.05 (2.74); p = 0.567), fat mass in kg (mean increase −0.07 (4.137); p = 0.356) or lean mass in kg (mean increase 0.20 (1.424); p = 0.636). Similarly, no statistically significant differences were observed between the two study periods for any of the nutrients studied, nor for energy intake (p > 0.05 in all cases). (4) Conclusions: After comprehensively assessing body composition and dietary intake of protein, fat, carbohydrates, and energy before and after COVID-19 lockdown in healthy adult women in Spain no changes in the parameters studied were observed during the period analyzed in the women examined.

Stepwise reduction of a corannulene-based helical molecular nanographene with Na metal.

The chemical reduction of a corannulene-based molecular nanographene, C76H64 (1), with Na metal in the presence of 18-crown-6 afforded the doubly-reduced state of 1. This reduction provokes a distortion of the helicene core and has a significant impact on the aromaticity of the system.

Synthetic chiral molecular nanographenes: the key figure of the racemization barrier.

Chirality is one of the most intriguing concepts of chemistry, involving living systems and, more recently, materials science. In particular, the bottom-up synthesis of molecular nanographenes endowed with one or several chiral elements is a current challenge for the chemical community. The wilful introduction of defects in the sp2 honeycomb lattice of molecular nanographenes allows the preparation of chiral molecules with tuned band-gaps and chiroptical properties. There are two requirements that a system must fulfill to be chiral: (i) lack of inversion elements (planes or inversion centres) and (ii) to be configurationally stable. The first condition is inherently established by the symmetry group of the structure, however, the limit between conformational and configurational isomers is not totally clear. In this feature article, the chirality and dynamics of synthetic molecular nanographenes, with special emphasis on their racemization barriers and, therefore, the stability of their chiroptical properties are discussed. The general features of nanographenes and their bottom-up synthesis, including the main defects inducing chirality in molecular nanographenes are firstly discussed. In this regard, the most common topological defects of molecular NGs as well as the main techniques used for determining their energy barriers are presented. Then, the manuscript is structured according to the dynamics of molecular nanographenes, classifying them in four main groups, depending on their respective isomerization barriers, as flexible, detectable, isolable and rigid nanographenes. In these sections, the different strategies used to increase the isomerization barrier of chiral molecular nanographenes that lead to configurationally stable nanographenes with defined chiroptical properties are discussed.

Initiating Electron Transfer in Doubly Curved Nanographene Upon Supramolecular Complexation of C60.

The formation of supramolecular complexes between C60 and a molecular nanographene endowed with both positive and negative curvatures is described. The presence of a corannulene moiety and the saddle shape of the molecular nanographene allows the formation of complexes with 1:1, 1:2, and 2:1 stoichiometries. The association constants for the three possible supramolecular complexes were determined by 1 H NMR titration. Furthermore, the stability of the three complexes was calculated by theoretical methods that also predict the photoinduced electron transfer from the curved nanographene to the electron acceptor C60 . Time-resolved transient absorption measurements on the ns-time scale showed that the addition of C60 to NG-1 solutions and photo-exciting them at 460 nm leads to the solvent-dependent formation of new species, in particular the formation of the one-electron reduced form of C60 in benzonitrile was observed.

Site-Specific Reduction-Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb+ Complexation.

The chemical reduction of π-conjugated bilayer nanographene 1 (C138 H120 ) with K and Rb in the presence of 18-crown-6 affords [K+ (18-crown-6)(THF)2 ][{K+ (18-crown-6)}2 (THF)0.5 ][C138 H122 3- ] (2) and [Rb+ (18-crown-6)2 ][{Rb+ (18-crown-6)}2 (C138 H122 3- )] (3). Whereas K+ cations are fully solvent-separated from the trianionic core thus affording a "naked" 1.3 - anion, Rb+ cations are coordinated to the negatively charged layers of 1.3 - . According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site-specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction-induced site-specific hydrogenation provokes dramatic changes in the (electronic) structure of 1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers.

Helically Arranged Chiral Molecular Nanographenes.

A benchtop solution-phase synthesis of molecular nanographenes composed of two orthogonal dibenzo[fg,ij]phenanthro[9,10,1,2,3-pqrst]pentaphene (DBPP) moieties covalently connected through a tetrafluorobenzene ring is described. The helical arrangement of these three covalently linked molecular fragments leads to the existence of a chiral axis which gives rise to a racemic mixture, even with the molecular moieties being symmetrically substituted. X-ray diffraction studies show that both enantiomers cocrystallize in a single crystal, and the racemic mixture can be resolved by chiral HPLC. Asymmetric substitution in DBPP moieties affords a pair of diastereoisomers whose rotational isomerization has been studied by 1H NMR. Additionally, the electrochemical and photophysical properties derived from these new molecular nanographenes reveal an electroactive character and a significant fluorescent behavior.

Long-Term Dietary and Physical Activity Interventions in the School Setting and Their Effects on BMI in Children Aged 6-12 Years: Meta-Analysis of Randomized Controlled Clinical Trials.

Preventive actions and potential obesity interventions for children are mainly researched throughout the school period, either as part of the school curricula or after regular school hours, via interventions mostly lasting less than 12 months. We aimed to perform a meta-analysis on randomized controlled clinical trials to evaluate the evidence of the efficacy of long-term school-based interventions in the management of childhood obesity in terms of BMI from a dietary and physical activity-based approach. Eleven randomized controlled clinical trials were examined using the random effects model, and the results showed that there were no significant effects associated with physical activity + nutrition intervention in school children aged 6-12 years, with a pooled standardized mean difference (SMD) (95% CI) of -0.00 (-0.05, 0.04). No effects were observed after subgroup analysis based on the intervention length. The findings from our study indicate that long-term school-based interventions on physical activity and dietary habits received by children aged 6-12 years seem to have no effect on BMI. However, the promotion of such interventions should not be discouraged, as they promote additional positive health outcomes for other domains of children's health.

Plasma Fatty Acids and Quantitative Ultrasound, DXA and pQCT Derived Parameters in Postmenopausal Spanish Women.

Different factors may contribute to the development of osteopenia or osteoporosis. Fatty acids are key nutrients for health, and a number of studies have reported an association between bone mineral density (BMD) and fatty acid intake. We aimed to investigate the relationships between serum levels of different fatty acids and bone parameters determined by quantitative bone ultrasound (QUS), peripheral quantitative computed tomography (pQCT), and dual-energy X-ray absorptiometry (DXA) in a sample of Spanish postmenopausal women. We enrolled a total of 301 postmenopausal women (median age 59 years; interquartile range (IQR) 7) in this study. All participants underwent full densitometric screening, including calcaneal quantitative ultrasound (QUS), peripheral quantitative computed tomography (pQCT), and dual-energy X-ray absorptiometry (DXA), as well as plasma fatty acid measurement. After adjustment for potential confounders, plasma n-3 polyunsaturated fatty acid (PUFA) levels correlated with BMD in the spine (r = 0.150; p = 0.014) and femoral neck (r = 0.143; p = 0.019). By multiple linear regression, an independent statistically significant positive relationship was observed between BMD in the spine and BMI (ß = 0.288; p = 0.001) as well as total plasma n-3 PUFAs (ß = 0.155; p = 0.009). The plasma n-3 PUFA level was also a significant and positive predictor of BMD at the femoral neck (ß = 0.146; p = 0.009). Independent risk factors for low BMD (T-score ≤ 1) were determined by logistic regression analysis, and a relatively high level of plasma n-3 PUFAs (OR = 0.751; 95% CI 0.587-0.960, p = 0.022) was identified as a protective factor against low bone mass. In this single-center sample of Spanish postmenopausal women, we reported a significant positive and statistically independent association between BMD and plasma levels of n-3 PUFAs.

Anger while driving in Mexico City.

This study aims to analyze the level of anger developed by drivers in Mexico City and also understand the behavior that those drivers use to express that anger, using four different survey methods. The first focuses on personal information, the second Driving Anger Expression Inventory (DAX), the third refers to a shorten version of Driving Anger Scale (DAS) and the fourth being the Dula Dangerous Driving Index (DDDI). These have previously been applied and validated in several different countries. The questionnaires were filled out online by 626 drivers. Using the data collected through the online platform, it was possible to identify the kind of reactions volunteers displayed while driving. Also, it was possible to identify that people in Mexico City developed anger depending on their driving area. Our analyses shows that in the Adaptive/Constructive Expression subscale, males and females show a significant difference in their mean score, with women express their anger in a more constructive way than males.

Chiral Molecular Carbon Nanostructures.

Chirality is a fascinating property present in naturally occurring and artificial molecules and materials, observable as chiroptical behavior. The emerging area of carbon nanostructures has undergone tremendous development, with a wide variety of carbon nanoforms reported over the last two decades. However, despite interest in merging chirality and nanocarbons, this has been successfully achieved only in empty fullerenes, whereas in other kinds of fullerenes or carbon nanostructures such as carbon nanotubes, graphene, and graphene quantum dots (GQDs), to name the most popular systems, it is almost unknown. Therefore, controlling chirality in carbon nanostructures currently represents a major challenge for the chemical community. In this Account, we show our progress in the synthesis of chiral molecular carbon nanostructures, namely, metallofullerenes, endohedral fullerenes, GQDs, and curved molecular nanographenes, by using asymmetric catalysis and both top-down and bottom-up chemical approaches. Furthermore, we bring in a new family of lesser-known molecular chiral bilayer nanographenes, where chirality is introduced from the starting helicene moiety and a single enantiomer of the nanographene is synthesized. Some important landmarks in the development of chiral molecular carbon nanostructures shown in this Account are the application of synthesis-tailored, enantiomerically pure metallofullerenes as catalysts for hydrogen transfer reactions and the use of endohedral fullerenes to determine the effect of the incarcerated molecule in the carbon cage on the cis-trans stereoisomerization of optically active pendent moieties. Furthermore, the first top-down synthesis of chiral GQDs by functionalization with chiral alcohols is also presented. An emerging alternative to GQDs, when the desire for purity and atomistic control outweighs the cost of multistep synthesis, is the bottom-up approach, in which molecular nanographenes are formed in precise sizes and shapes and enantiomeric control is feasible. In this regard, a singular and amazing example is given by our synthesis of a single enantiomer of the first chiral bilayer nanographene, which formally represents a new family of molecular nanographenes with chirality controlled and maintained throughout their syntheses. The aforementioned synthetic chiral nanostructures represent groundbreaking nanocarbon systems where chirality is a further dimension of structural control, paving the way to a new scenario for carbon nanoforms in which chirality selection determines the properties of these novel carbon-based materials. Fine-tuning of such properties is envisioned to impact biomedical and materials science applications.

Adherence to a Mediterranean Diet and Bone Mineral Density in Spanish Premenopausal Women.

The Mediterranean diet (MD) has been associated with an improvement in health and an increase in longevity. Certain components of a MD can play a role in the prevention of osteoporosis and/or hip fracture. We investigated the association between the degree of adherence to a MD and bone mineral density (BMD) measured in several bone areas in a population of Spanish premenopausal women. We analyzed 442 premenopausal women aged 42.73 ± 6.67 years. Bone measurements were obtained using quantitative bone ultrasound (QUS) for the phalanx, dual energy X-ray absorptiometry (DXA) for the lumbar spine, Ward's triangle, trochanter, and hip, and peripheral quantitative computed tomography (pQCT) for the non-dominant distal forearm. MD adherence was evaluated with MedDietScore. Amplitude-dependent speed of sound (Ad-SOS), BMD, and volumetric bone mineral density (vBMD) (total, trabecular, and cortical bone density) were positively associated with higher adherence to the MD (p < 0.05). Adherence to the MD was significantly associated with QUS, BMD, and vBMD in multiple regression analysis; QUS: Ad-SOS (m/s) ß = 0.099 (p = 0.030); BMD (g/cm²): femur neck ß = 0.114 (p = 0.010) and Ward's triangle ß = 0.125 (p = 0.006); vBMD (mg/cm³): total density ß = 0.119 (p = 0.036), trabecular density ß = 0.120 (p = 0.035), and cortical density ß = 0.122 (p = 0.032). We conclude that the adherence to the MD was positively associated with better bone mass in Spanish premenopausal women.

Enantioselective Addition of Alkynyl Ketones to Nitroolefins Assisted by Brønsted Base/H-Bonding Catalysis.

Various sets of enolizable alkynyl ketones (including methyl ynones with α-aryl, α-alkenyl, and α-alkoxy groups) were able to react smoothly with nitroolefins with the assistance of bifunctional Brønsted base/H-bond catalysts to provide adducts with two consecutive tertiary stereocenters in a highly diastereo- and enantioselective fashion. Further transformation of the obtained adducts into optically active acyclic and polycyclic molecules, including some with intricate carbon skeletons, was also demonstrated.

Selling the product: Strategies to increase recruitment and retention of Spanish-speaking Latinos in biomedical research.

INTRODUCTION: The Latino population in the US is rapidly growing and faces profound health disparities; however, engagement of Latinos in biomedical research remains low. Our community-based participatory research (CBPR) partnership has recruited 2,083 Spanish-speaking Latinos into 21 studies over 15 years. We sought to identify and describe the strategies we have used to successfully recruit and retain Spanish-speaking Latinos in research. METHODS: We abstracted and analyzed data from archived study notes, progress reports, team meeting minutes, and in-depth interviews conducted annually from CBPR partnership members. We used a nominal group process to refine and prioritize strategies. RESULTS: Overall, 13 recruitment strategies and 12 retention strategies emerged. These strategies relied on the creativity and perseverance of the study team and partners. CONCLUSIONS: It is essential that we develop and disseminate effective recruitment and retention strategies that engage Latinos in biomedical research to reduce health disparities and promote health equity.