Exploring the Mechanisms behind Non-aromatic Fluorescence with the Density Functional Tight Binding Method.

Recent experimental findings reveal nonconventional fluorescence emission in biological systems devoid of conjugated bonds or aromatic compounds, termed non-aromatic fluorescence (NAF). This phenomenon is exclusive to aggregated or solid states and remains absent in monomeric solutions. Previous studies focused on small model systems in vacuum show that the carbonyl stretching mode along with strong interaction of short hydrogen bonds (SHBs) remains the primary vibrational mode explaining NAF in these systems. In order to simulate larger model systems taking into account the effects of the surrounding environment, in this work we propose using the density functional tight-binding (DFTB) method in combination with non-adiabatic molecular dynamics (NAMD) and the mixed quantum/molecular mechanics (QM/MM) approach. We investigate the mechanism behind NAF in the crystal structure of l-pyroglutamine-ammonium, comparing it with the related nonfluorescent amino acid l-glutamine. Our results extend our previous findings to more realistic systems, demonstrating the efficiency and robustness of the proposed DFTB method in the context of NAMD in biological systems. Furthermore, due to its inherent low computational cost, this method allows for a better sampling of the nonradiative events at the conical intersection which is crucial for a complete understanding of this phenomenon. Beyond contributing to the ongoing exploration of NAF, this work paves the way for future application of this method in more complex biological systems such as amyloid aggregates, biomaterials, and non-aromatic proteins.

Medicalização da alimentação e da nutrição: aproximações conceituais / Medicalization of food and nutrition: conceptual approach

Resumo O objetivo deste estudo foi identificar conceitos e temáticas centrais da medicalização da alimentação e da nutrição. Para tanto, realizou-se revisão de busca sistematizada seguindo o método Systematic-Search Flow em sete bases de dados, combinando a palavra-chave "medicali?ation" com nutrition*, diet*, food, nourishment e eat*. Após a aplicação dos critérios de inclusão e de exclusão, foram selecionados 17 documentos que compuseram o portfólio de análise. A leitura destes documentos permitiu pensar em categorias, sendo elas: medicalização da alimentação: dispositivos de controle do corpo e do comportamento alimentar; dispositivos de prevenção e programas de educação nutricional; alimentos como medicamentos e Nutrição Personalizada. Em todas, foi possível identificar estratégias pelas quais a alimentação e a nutrição foram reduzidas ao olhar da biomedicina, desconsiderando outras dimensões do alimentar-se. Essa redução ocorreu por meio: a) da prescrição de normas de comportamento e dietas; b) de práticas preventivas que moralizam comportamentos considerados de risco, causando estigmatização e culpabilização dos indivíduos pelas suas doenças; c) da concepção dos alimentos como se fossem medicamentos; d) da prescrição individualizada de dietas, de acordo com a Nutrição Personalizada, comprometendo a compreensão do alimentar-se a partir dos aspectos políticos, culturais, históricos e sociais.

Abstract This study aimed to identify concepts and central themes of the medicalization of food and nutrition. To this end, a systematized search review following the Systematic-Search Flow method was conducted in seven databases, combining the keyword "medicali?ation" with nutrition*, diet*, food, nourishment and eat*. After applying the inclusion and exclusion criteria, 17 documents were selected to compose the analysis portfolio. The reading of these documents allowed us to think of categories, as follows: medicalization of food: devices to control the body and eating behavior; prevention devices and nutrition education programs; food as medicine and Personalized Nutrition. In all of them, it was possible to identify strategies through which food and nutrition were reduced to the biomedical view, disregarding other dimensions of eating. This reduction occurred through a) the prescription of behavioral norms and diets; b) preventive practices that moralize behaviors considered risky, causing stigmatization and blaming individuals for their diseases; c) the conception of food as if it were medicine; d) the individualized prescription of diets, according to Personalized Nutrition, compromising the understanding of eating from political, cultural, historical, and social aspects.

Benchmark Data Set of Crystalline Organic Semiconductors.

This work reports a Benchmark Data set of Crystalline Organic Semiconductors to test calculations of the structural and electronic properties of these materials in the solid state. The data set contains 67 crystals consisting of mostly rigid molecules with a single dominant conformer, covering the majority of known structural types. The experimental crystal structure is available for the entire data set, whereas zero-temperature unit cell volume can be reliably estimated for a subset of 28 crystals. Using this subset, we benchmark r2SCAN-D3 and PBE-D3 density functionals. Then, for the entire data set, we benchmark approximate density functional theory (DFT) methods, including GFN1-xTB and DFTB3(3ob-3-1), with various dispersion corrections against r2SCAN-D3. Our results show that r2SCAN-D3 geometries are accurate within a few percent, which is comparable to the statistical uncertainty of experimental data at a fixed temperature, but the unit cell volume is systematically underestimated by 2% on average. The several times faster PBE-D3 provides an unbiased estimate of the volume for all systems except for molecules with highly polar bonds, for which the volume is substantially overestimated in correlation with the underestimation of atomic charges. Considered approximate DFT methods are orders of magnitude faster and provide qualitatively correct but overcompressed crystal structures unless the dispersion corrections are fitted by unit cell volume.

Photoresponse of Solution-Synthesized Graphene Nanoribbon Heterojunctions on Diamond Indicating Phototunable Photodiode Polarity.

Graphene nanoribbon heterostructures and heterojunctions have attracted interest as next-generation molecular diodes with atomic precision. Their mass production via solution methods and prototypical device integration remains to be explored. Here, the bottom-up solution synthesis and characterization of liquid-phase-processable graphene nanoribbon heterostructures (GNRHs) are demonstrated. Joint photoresponsivity measurements and simulations provide evidence of the structurally defined heterostructure motif acting as a type-I heterojunction. Real-time, time-dependent density functional tight-binding simulations further reveal that the photocurrent polarity can be tuned at different excitation wavelengths. Our results introduce liquid-phase-processable, self-assembled heterojunctions for the development of nanoscale diode circuitry and adaptive hardware.

Host traits, ownership behaviour and risk factors of SARS-CoV-2 infection in domestic pets in Mexico.

SARS-CoV-2 can infect pets under natural conditions, which raises questions about the risk factors related to the susceptibility of these animals to infection. The status of pet infection by SARS-CoV-2 in Mexico is not well-understood. We aimed to estimate the frequency of positive household cats and dogs to viral RNA and antibodies for SARS-CoV-2 during the second wave of human infections in Mexico, and to recognize the major risk factors related to host and pet ownership behaviour. We evaluated two study groups, cats and dogs from COVID-19-infected/-suspected households (n = 44) and those admitted for veterinary care for any reason at several veterinary hospitals in Puebla City, Mexico (n = 91). Using RT-PCR, we identified the presence of SARS-CoV-2 RNA in swabs of four dogs (18.18%) and zero cats in COVID-19-infected/-suspected households; within this group, 31.82% of dogs and 27.27% of cats were tested IgG ELISA-positive; and neutralizing antibodies were detected in one dog (4.55%) and two cats (9.09%). In the random group (pets evaluated at private clinics and veterinary teaching hospital), 25.00% of dogs and 43.59% of cats were ELISA-positive and only one cat showed neutralizing antibodies (2.56%). Older than 4-year-old, other pets at home, and daily cleaning of pet dish, were each associated with an increase in SARS-CoV-2 infection (p < 0.05). Allowing face lick, sharing bed/food with pets and owner tested positive or suspected COVID-19 were not significant risk factors, but more than 4 h the owner spent away from home during the lockdown for COVID-19 (OR = 0.37, p = 0.01), and outdoor pet food tray (OR = 0.32, p = 0.01) significantly decreased the risks of SARS-CoV-2 infection in pets, suggesting that time the owner spends with their pet is an important risk factor.

Fano Resonance and Incoherent Interlayer Excitons in Molecular van der Waals Heterostructures.

Complex van der Waals heterostructures from layered molecular stacks are promising optoelectronic materials offering the means to efficient, modular charge separation and collection layers. The effect of stacking in the electrodynamics of such hybrid organic-inorganic two-dimensional materials remains largely unexplored, whereby molecular scale engineering could lead to advanced optical phenomena. For instance, tunable Fano engineering could make possible on-demand transparent conducting layers or photoactive elements, and passive cooling. We employ an adapted Gersten-Nitzan model and real time time-dependent density functional tight-binding to study the optoelectronics of self-assembled monolayers on graphene nanoribbons. We find Fano resonances that cause electromagnetic induced opacity and transparency and reveal an additional incoherent process leading to interlayer exciton formation with a characteristic charge transfer rate. These results showcase hybrid van der Waals heterostructures as paradigmatic 2D optoelectronic stacks, featuring tunable Fano optics and unconventional charge transfer channels.

Landscape Anthropization Affects Mosquito Diversity in a Deciduous Forest in Southeastern Mexico.

Mosquitoes (Diptera: Culicidae) are considered the group of insects that most impacts human health. Land use change, conversion of conserved sites into agricultural environments, urbanization, defaunation, and introduction of domestic animals can affect mosquito diversity positively or negatively, increasing the risk of transmission of zoonotic diseases. Here, we describe the diversity of adult mosquitoes in two environments (deciduous forest and anthropized zone) over 2 yr (2014-2016), using eight CDC traps at each site in three climatic seasons (rainy, cold, and dry). We captured 795 individuals belonging to 22 species. We constructed rank-abundance curves to determine spatial and temporal changes in the mosquito communities. We measured alpha diversity using the Shannon index (H'), Shannon exponential (eH) and Simpson dominance (Ds), and beta diversity using Jaccard's coefficient of similarity (Ij). The most abundant species were Culex quinquefasciatus (40.5%), Culex coronator (18.3%), and Anopheles pseudopunctipennis (12.4%). The highest mosquito diversity was in the deciduous forest during the rainy season. Beta diversity analysis showed that species overlap varied among climatic seasons, with the sites sharing 65% species during the rainy season, but only 33% of species during the dry season. We found differences in the diversity of mosquitoes at the two sites, and the mosquito assemblage of the anthropized zone was significantly different from that of the deciduous forest.

Photoinduced charge-transfer in chromophore-labeled gold nanoclusters: quantum evidence of the critical role of ligands and vibronic couplings.

The electron flow between a metallic aggregate and an organic molecule after excitation with light is a crucial step on which hybrid photovoltaic nanomaterials are based. So far, designing such devices with the help of theoretical approaches has been heavily limited by the computational cost of quantum dynamics models able to track the evolution of the excited states over time. In this article, we present the first application of the time-dependent density functional tight-binding (TD-DFTB) method for an experimental nanometer-sized gold-organic system consisting of a hexyl-protected Au25 cluster labelled with a pyrene fluorophore, in which the fluorescence quenching of the pyrene is attributed to the electron transfer from the metallic cluster to the dye. The full quantum rationalization of the electron transfer is attained through quantum dynamics simulations, highlighting the crucial role of the protecting ligand shell in electron transfer, as well as the coupling with nuclear movement. This work paves the way towards the fast and accurate theoretical design of optoelectronic nanodevices.

Effects of landscape anthropization on sylvatic mosquito assemblages in a rainforest in Chiapas, Mexico.

Global change and ecosystem transformation at regional and local scales during recent decades have facilitated the exponential increase of outbreaks of mosquito-borne diseases. Mosquito-borne pathogens are responsible for millions of infections, mainly in tropical regions where marginalized human populations are located, and where in recent years processes of landscape anthropization have occurred. Anthropogenic landscape transformation is known to change species assemblages. However, the magnitude of these effects is largely unknown, and the effects of anthropogenic landscape transformation on sylvatic mosquito assemblages are poorly known in Mexican ecosystems. We evaluate how mosquito abundance, richness, and diversity change along a gradient of three human-modified landscapes-one highly anthropized, one moderately anthropized, and one slightly anthropized-within a tropical forest matrix in a Protected Natural Area in Chiapas. A total of 4 538 mosquitoes belonging to 23 species were captured and identified at the three sites. We found differences in the structure and abundance of the three mosquito assemblages. The species assemblage of the highly anthropized site was significantly different from the other sites, and the relative abundance of the assemblages increased with landscape anthropization. Our results suggest that landscape anthropization alters the composition and structure of mosquito assemblages, modifying the abundance and species richness of mosquitoes associated with sylvatic ecosystems. This could support the hypothesis of intermediate disturbance that suggests the diversity is maximized when late and early successional species coexist in these ecosystems. This information is essential to understand the ecology of potential sylvatic vectors and the environmental factors that are involved in the emergence and re-emergence of mosquito-borne diseases.

Assemblage variation of mosquitoes (Diptera: Culicidae) in different land use and activity periods within a lowland tropical forest matrix in Campeche, Mexico.

Most mosquito species are active during a certain part of the day, but climatic factors such as light intensity and relative humidity play an important role in the control of their activity. We selected three types of land use that were sampled in state of Campeche in 2018 (low semi-evergreen forest, secondary low semi-evergreen forest, and mango plantation), using ten CDC light traps baited with CO2 , that were active during nine hours of three activity periods (dawn, noon, and nightfall). A GLM was used to investigate changes in the assembly of mosquitoes between different types of land use and temporal variations. Rank abundance curves were used to detect changes in the spatial and activity period of the mosquitoes and we then calculated the Exponential Shannon Index. A total of 6,110 mosquitoes belonging to 23 species were captured. The greatest richness and abundance were found in the secondary low semi-evergreen forest, with greater richness and lower abundance than the mango plantation which showed more abundance. Of the activity periods, dusk had the greatest abundance and richness followed by dawn and finally noon.

A Real-Time Time-Dependent Density Functional Tight-Binding Implementation for Semiclassical Excited State Electron-Nuclear Dynamics and Pump-Probe Spectroscopy Simulations.

The increasing need to simulate the dynamics of photoexcited molecular systems and nanosystems in the subpicosecond regime demands new efficient tools able to describe the quantum nature of matter at a low computational cost. By combining the power of the approximate DFTB method with the semiclassical Ehrenfest method for nuclear-electron dynamics, we have achieved a real-time time-dependent DFTB (TD-DFTB) implementation that fits such requirements. In addition to enabling the study of nuclear motion effects in photoinduced charge transfer processes, our code adds novel features to the realm of static and time-resolved computational spectroscopies. In particular, the optical properties of periodic materials such as graphene nanoribbons or the use of corrections such as the "LDA+U" and "pseudo SIC" methods to improve the optical properties in some systems can now be handled at the TD-DFTB level. Moreover, the simulation of fully atomistic time-resolved transient absorption spectra and impulsive vibrational spectra can now be achieved within reasonable computing time, owing to the good performance of the implementation and a parallel simulation protocol. Its application to the study of UV/visible light-induced vibrational coherences in molecules is demonstrated and opens a new door into the mechanisms of nonequilibrium ultrafast phenomena in countless materials with relevant applications.

Improving Physical Activity Levels and Psychological Variables on University Students in the Contemplation Stage.

This study aimed to investigate the effects of a physical activity intervention, based on self-determination theory and the transtheoretical model, on university students in the contemplation stage. PARTICIPANTS: 42 students, in the contemplation stage at baseline, were randomly assigned to an experimental group (16 women, 2 men; M age = 19.1 ± 1.15) and a control group (18 women, 2 men; M age = 20.1 ± 5.7). METHODS: Physical activity was measured at different moments by accelerometry. Other cognitive variables were measured by self-reported scales. RESULTS: We did not find any significant increases in students' physical activity in favor of the intervention group. Intragroup analyses indicate that the intervention has an effect on physical activity (moderate-to-vigorous physical activity), basic psychological needs, and intrinsic and extrinsic motivation. CONCLUSIONS: Results partially demonstrate that applying social cognitive theories seems to be effective in improving physical activity and cognitive variables in university students in the contemplation stage.

Wearable Sensors for Measuring Movement in Short Sessions of Mindfulness Sitting Meditation: A Pilot Study.

Mindfulness techniques are useful tools in health and well-being. To improve and facilitate formal training, beginners need to know if they are in a stable sitting posture and if they can hold it. Previous monitoring studies did not consider stability during sitting meditation or were specific for longer traditional practices. In this paper, we have extended and adapted previous studies to modern mindfulness practices and posed two questions: (a) Which is the best meditation seat for short sessions? In this way, the applications of stability measures are expanded to meditation activities, in which the sitting posture favors stability, and (b) Which is the most sensitive location of an accelerometer to measure body motion during short meditation sessions? A pilot study involving 31 volunteers was conducted using inertial sensors. The results suggest that thumb, head, or infraclavicular locations can be chosen to measure stability despite the habitual lumbar or sacral region found in the literature. Another important finding of this study is that zafus, chairs, and meditation benches are suitable for short meditation sessions in a sitting posture, although the zafu seems to allow for fewer postural changes. This finding opens new opportunities to design very simple and comfortable measuring systems.

Trap-Door-Like Irreversible Photoinduced Charge Transfer in a Donor-Acceptor Complex.

For efficient conversion of light into useful energy sources, it is very important to study and describe the first steps of primary charge-transfer process in natural structures and artificial devices. The time scale of these processes in artificial photosynthetic and photovoltaic devices is on the order of femto- to picoseconds and involves vibronic coupling of electrons and nuclei and also nuclear alleviation to enhance charge separation. Here we present an atomistic description of the photoexcited electron dynamics in a noncovalently bonded system formed by an hydrogenated nanodiamond as donor and a perylene diimide as an acceptor. The complex shows extremely fast charge transfer, separation, and stabilization within 90 fs. This stabilization is purely electronic in nature. To the best of our knowledge, these results show for the first time that it is possible to stabilize charge without polaron formation or nuclear relaxation, reaching a steady state enhanced by a pure electronic reorganization.

Expand your body when you look at yourself: The role of the posture in a mirror exposure task.

Mirror exposure (ME) is one of the main components of the treatment of patients with eating disorders symptomatology and it has shown its effectiveness in improving several outcomes (e.g., body dissatisfaction). However, the study as to what body posture should be adopted to maximize its effectiveness has been neglected. From embodied cognition and emotion theories, the adoption of an expansive (vs. contractive) body posture has been associated with positive changes in cognitive and emotional responses. The objective of this study was to analyze the effect of adopting an expansive (vs. contractive) posture before an ME task on body-related emotions and cognitions, as well as to analyze the possible moderator and mediator variables of these relationships. The sample was composed of 68 women (age: M = 21.74, SD = 3.12) with high scores on body dissatisfaction. Participants were randomly assigned to the expansive or contractive condition, where the openness of the arms/legs and the back position were manipulated. Posture was monitored by an electronic device and participants filled out several self-reported measures. ANCOVAs, moderation, mediation, and moderated mediated analyses were performed. Results showed that women in the expansive condition showed higher positive emotions after the ME. Moreover, exploratory analyses showed that adopting an expansive posture improved positive emotions, leading to improvements in negative emotions, body image satisfaction, and appraisal of the person's own body. Psychological interventions should explore the value of holding an expansive posture before the ME in women with body dissatisfaction.

Potential Sympatric Vectors and Mammalian Hosts of Venezuelan Equine Encephalitis Virus in Southern Mexico.

Arboviruses are important zoonotic agents with complex transmission cycles and are not well understood because they may involve many vectors and hosts. We studied sympatric wild mammals and hematophagous mosquitoes having the potential to act as hosts and vectors in two areas of southern Mexico. Mosquitoes, bats, and rodents were captured in Calakmul (Campeche) and Montes Azules (Chiapas), between November 2010 and August 2011. Spleen samples from 146 bats and 14 rodents were tested for molecular evidence of Venezuelan equine encephalitis virus (VEEV), eastern equine encephalitis virus (EEEV), western equine encephalitis virus (WEEV), and West Nile virus (WNV) using PCR protocols. Bat ( Artibeus lituratus , Carollia sowelli , Glossophaga soricina , and Sturnira parvidens) and rodent ( Sigmodon hispidus and Oryzomys alfaroi ) species were positive for VEEV. No individuals were positive for WNV, EEEV, or WEEV. A total of 1,298 mosquitoes were collected at the same sites, and five of the mosquito species collected were known VEEV vectors (Aedes fulvus, Mansonia indubitans, Psorophora ferox, Psorophora cilipes, and Psorophora confinnis). This survey simultaneously presents the first molecular evidence, to our knowledge, of VEEV in bats and rodents from southern Mexico and the identification of potential sympatric vectors. Studies investigating sympatric nonhuman hosts, vectors, and arboviruses must be expanded to determine arboviral dynamics in complex systems in which outbreaks of emerging and reemerging zoonoses are continuously occurring.

Combining novelty detectors to improve accelerometer-based fall detection.

Research on body-worn sensors has shown how they can be used for the detection of falls in the elderly, which is a relevant health problem. However, most systems are trained with simulated falls, which differ from those of the target population. In this paper, we tackle the problem of fall detection using a combination of novelty detectors. A novelty detector can be trained only with activities of daily life (ADL), which are true movements recorded in real life. In addition, they allow adapting the system to new users, by recording new movements and retraining the system. The combination of several detectors and features enhances performance. The proposed approach has been compared with a traditional supervised algorithm, a support vector machine, which is trained with both falls and ADL. The combination of novelty detectors shows better performance in a typical cross-validation test and in an experiment that mimics the effect of personalizing the classifiers. The results indicate that it is possible to build a reliable fall detector based only on ADL.

One-Shot Learning of Human Activity With an MAP Adapted GMM and Simplex-HMM.

This paper presents a novel activity class representation using a single sequence for training. The contribution of this representation lays on the ability to train an one-shot learning recognition system, useful in new scenarios where capturing and labeling sequences is expensive or impractical. The method uses a universal background model of local descriptors obtained from source databases available on-line and adapts it to a new sequence in the target scenario through a maximum a posteriori adaptation. Each activity sample is encoded in a sequence of normalized bag of features and modeled by a new hidden Markov model formulation, where the expectation-maximization algorithm for training is modified to deal with observations consisting in vectors in a unit simplex. Extensive experiments in recognition have been performed using one-shot learning over the public datasets Weizmann, KTH, and IXMAS. These experiments demonstrate the discriminative properties of the representation and the validity of application in recognition systems, achieving state-of-the-art results.

Photoinduced charge-transfer dynamics simulations in noncovalently bonded molecular aggregates.

The rational design of new materials as prototype systems for organic solar cells remains challenging. Perylene diimide has emerged as a promising material to replace fullerene derivatives because of its synthetic flexibility, leading to the manipulation of their optical properties. As a result of their fused aromatic core that favors π-π stacking interactions, the aggregation of these molecules can reach highly ordered nanostructures as one-dimensional nanofibers, with a fast photoinduced charge transfer mechanism. In this article, we present an atomistic description of the photoexcited exciton dynamics in noncovalently bonded perylene diimides by time integration of the electron density in the presence of external time varying electric fields. We show that our approach is able to capture and explain the physics that underlies the charge transport mechanism through perylene diimide aggregates.