The Role of Hydrogen Bonding in the Raman Spectral Signals of Caffeine in Aqueous Solution.

The identification and quantification of caffeine is a common need in the food and pharmaceutical industries and lately also in the field of environmental science. For that purpose, Raman spectroscopy has been used as an analytical technique, but the interpretation of the spectra requires reliable and accurate computational protocols, especially as regards the Resonance Raman (RR) variant. Herein, caffeine solutions are sampled using Molecular Dynamics simulations. Upon quantification of the strength of the non-covalent intermolecular interactions such as hydrogen bonding between caffeine and water, UV-Vis, Raman, and RR spectra are computed. The results provide general insights into the hydrogen bonding role in mediating the Raman spectral signals of caffeine in aqueous solution. Also, by analyzing the dependence of RR enhancement on the absorption spectrum of caffeine, it is proposed that the sensitivity of the RR technique could be exploited at excitation wavelengths moderately far from 266 nm, yet achieving very low detection limits in the quantification caffeine content.

Guías de primeros auxilios en salud mental para Argentina y Chile: un reporte del estudio de adaptación de las guías australianas.

Introducción: Los problemas de salud mental en la comunidad representan una preocupación global creciente, intensificada desde la pandemia por coronavirus y gracias a una mayor conciencia respecto de su extensión y del bajo nivel de atención que recibieron a lo largo del tiempo. En Australia se crearon las primeras guías de primeros auxilios en salud mental para promover un mayor conocimiento de temas de salud mental en la población general, brindar apoyo oportuno, facilitar el acceso a los servicios de salud por esta problemática, y disminuir el estigma asociado al padecimiento mental. Método: Un consorcio de investigadores de Australia, Argentina y Chile, entre marzo de 2020 y mayo de 2023, realizó la adaptación cultural de cinco guías (consumo problemático de alcohol, depresión, riesgo de suicidio, trauma, y psicosis) siguiendo la metodología de consenso Delphi. Profesionales expertos en cada uno de los temas y personas con experiencia vivida  (propia o como cuidadores informales) conformaron sendos paneles con miembros de Argentina y de Chile. En dos rondas de consulta evaluaron los ítems provenientes de las guías de Australia y opinaron sobre su pertinencia para formar parte de las guías locales. Adicionalmente, sugirieron ítems que no estaban contemplados en las guías australianas. Resultados: El presente reporte presenta el detalle de la metodología empleada y los resultados más significativos de cada una de las cinco guías adaptadas y, particularmente, su aplicabilidad para Argentina y Chile. Sobresale la aceptación general del rol del asistente de primeros auxilios en salud mental, aunque también con limitaciones en el rol y funciones en favor del privilegio de profesionales de la salud. Las recomendaciones de auto-ayuda fueron mayoritariamente no aceptadas por los expertos locales, sugiriendo desconfianza respecto de estas estrategias. Otras recomendaciones específicas para cada una de las guías se describen y analizan en este reporte. Conclusiones: Se requiere un estudio de la implementación de la capacitación en base a estas guías para realizar ulteriores adaptaciones y determinar su utilidad local.

How to treat mixed behavior segments in supervised machine learning of behavioural modes from inertial measurement data.

The application of supervised machine learning methods to identify behavioural modes from inertial measurements of bio-loggers has become a standard tool in behavioural ecology. Several design choices can affect the accuracy of identifying the behavioural modes. One such choice is the inclusion or exclusion of segments consisting of more than a single behaviour (mixed segments) in the machine learning model training data. Currently, the common practice is to ignore such segments during model training. In this paper we tested the hypothesis that including mixed segments in model training will improve accuracy, as the model would perform better in identifying them in the test data. We test this hypothesis using a series of data simulations on four datasets of accelerometer data coupled with behaviour observations, obtained from four study species (Damaraland mole-rats, meerkats, olive baboons, polar bears). Results show that when a substantial proportion of the test data are mixed behaviour segments (above ~ 10%), including mixed segments in machine learning model training improves the accuracy of classification. These results were consistent across the four study species, and robust to changes in segment length, sample size, and degree of mixture within the mixed segments. However, we also find that in some cases (particularly in baboons) models trained with mixed segments show reduced accuracy in classifying test data containing only single behaviour (pure) segments, compared to models trained without mixed segments. Based on these results, we recommend that when the classification model is expected to deal with a substantial proportion of mixed behaviour segments (> 10%), it is beneficial to include them in model training, otherwise, it is unnecessary but also not harmful. The exception is when there is a basis to assume that the training data contains a higher rate of mixed segments than the actual (unobserved) data to be classified-such a situation may occur particularly when training data are collected in captivity and used to classify data from the wild. In this case, excess inclusion of mixed segments in training data should probably be avoided.

Transient Structural Properties of the Rho GDP-Dissociation Inhibitor.

Rho GTPases, master spatial regulators of a wide range of cellular processes, are orchestrated by complex formation with guanine nucleotide dissociation inhibitors (RhoGDIs). These have been thought to possess an unstructured N-terminus that inhibits nucleotide exchange of their client upon binding/folding. Via NMR analyses, molecular dynamics simulations, and biochemical assays, we reveal instead pertinent structural properties transiently maintained both, in the presence and absence of the client, imposed onto the terminus context-specifically by modulating interactions with the surface of the folded C-terminal domain. These observations revise the long-standing textbook picture of the GTPases' mechanism of membrane extraction. Rather than by a disorder-to-order transition upon binding of an inhibitory peptide, the intricate and highly selective extraction process of RhoGTPases is orchestrated via a dynamic ensemble bearing preformed transient structural properties, suitably modulated by the specific surrounding along the multi-step process.

Computational Spectroscopy of Aqueous Solutions: The Underlying Role of Conformational Sampling.

Fully atomistic multiscale polarizable quantum mechanics (QM)/molecular mechanics (MM) approaches, combined with techniques to sample the solute-solvent phase space, constitute the most accurate method to compute spectral signals in aqueous solution. Conventional sampling strategies, such as classical molecular dynamics (MD), may encounter drawbacks when the conformational space is particularly complex, and transition barriers between conformers are high. This can lead to inaccurate sampling, which can potentially impact the accuracy of spectral calculations. For this reason, in this work, we compare classical MD with enhanced sampling techniques, i.e., replica exchange MD and metadynamics. In particular, we show how the different sampling techniques affect computed UV, electronic circular dichroism, nuclear magnetic resonance shielding, and optical rotatory dispersion of N-acetylproline-amide in aqueous solution. Such a system is a model peptide characterized by complex conformational variability. Calculated values suggest that spectral properties are influenced by solute conformers, relative population, and solvent effects; therefore, particular care needs to be paid for when choosing the sampling technique.

Encapsulation of charged halogens by the 512 water cage.

This study focuses on the encapsulation of the entire series of halides by the 512 cage of twenty water molecules and on the characterization of water to water and water to anion interactions. State-of-the-art computations are used to determine equilibrium geometries, energy related quantities, and thermal stability towards dissociation and to dissect the nature and strength of intermolecular interactions holding the clusters as stable units. Two types of structures are revealed: heavily deformed cages for F- indicating a preference for microsolvation, and slightly deformed cages for the remaining anions indicating a preference for encapsulation. The primary variable dictating the properties of the clusters is the charge density of the central halide, with the most severe effects observed for the F- case. For the remaining halides, the anion may be safely viewed as a sort of "big electron" with little local disruptive power, enough to affect the network of non-covalent hydrogen bonds in the cage, but not enough to break it. Gibbs energies for dissociation either into cavity and halide or into water molecules and halide suggest that, in a similar way as to methane clathrate, a more weakly bonded complex that has been detected in the gas phase, all halide containing clathrate-like structures should be amenable to experimental detection in the gas phase at moderate temperature and pressure conditions.

When Tautomers Matter: UV-Vis Absorption Spectra of Hypoxanthine in Aqueous Solution from Fully Atomistic Simulations.

The UV-Vis spectrum of the solvated purine derivative Hypoxanthine (HYX) is investigated using the Quantum Mechanics/Fluctuating Charges (QM/FQ) multiscale approach combined with a sampling of configurations through atomistic Molecular Dynamics (MD) simulations. Keto 1H7H and 1H9H tautomeric forms of HYX are the most stable in aqueous solution and form different stable complexes with the surrounding water molecules, ultimately affecting the electronic absorption spectra. The final simulated spectrum resulting from the combination of the individual spectra of tautomers agrees very well with most of the characteristics in the measured spectrum. The importance of considering the effect of the solute tautomers and, in parallel, the contribution of the different solvent arrangements around the solute when modeling spectral properties, is highlighted. In addition, the high quality of the computed spectra leads to suggesting an alternative way for acquiring tautomeric populations from combined computational/experimental spectra.

Lack of Specific Immune Response after Five Doses of mRNA SARS-CoV-2 Vaccine in a Patient with CD4+ T-Cell Lymphopenia but Preserved Responses to CMV.

Immunogenicity of SARS-CoV-2 mRNA vaccines is highly heterogeneous in patients with inborn errors of immunity (IEIs). This case report analyzes the immune response to mRNA COVID-19 two-dose primary vaccination followed by three boosters in an IEI patient with marked CD4+ T-cell cytopenia and diminished thymic output, in comparison with that raised against latent, chronic cytomegalovirus (CMV) infection. Serum IgG antibodies anti-spike (S) protein of SARS-CoV-2 and anti-CMV were both determined by chemiluminescent microparticle immunoassays (CMIAs). SARS-CoV-2 and CMV memory CD4+ T-cell responses were simultaneously evaluated in vitro using an activation-induced marker (AIM) assay via multicolor flow cytometry. Throughout the 2-year follow-up that included the administration of five doses of SARS-CoV-2 mRNA vaccines, cellular anti-SARS-CoV-2-specific responses remained consistently negative, with extremely weak humoral responses, while the patient showed in vitro persistent CD4+ T-cell reactivity to CMV peptides and high-IgG CMV-specific titers. The assessment of immune responses to vaccines and prevalent viruses is essential in IEI patients in order to take adequate preventive measures.

Development of mental health first-aid guidelines for a person after a potentially traumatic event: A Delphi expert consensus study in Argentina and Chile.

BACKGROUND: Exposure to potentially traumatic events increases the risk of a person developing a mental disorder. Training community members to offer support to a person during and after a traumatic situation may help lower this risk. This study reports on the cultural adaptation of Australian mental health first aid guidelines for individuals exposed to a potentially traumatic event to the Chilean and Argentinian context. METHODS: A Delphi expert consensus study was conducted with two panels of experts, one of people with lived experience of trauma (either their own or as a carer; n = 26) and another one of health professionals (n = 41). A total of 158 items, drawn from guidelines developed by Australian experts in 2019, were translated to Spanish and evaluated in a two-round survey process. The panellists were asked to rate each item on a five-point Likert scale; statements were included in the final guidelines if 80% of both panels endorsed the item as "essential" or "important". RESULTS: Consensus was achieved on 142 statements over two survey rounds. A total of 102 statements were included from the English-language guidelines, and 40 locally generated statements were accepted in the second round. Local experts endorsed a larger number of items compared to their counterparts in Australia and emphasised the importance of acknowledging the first aider's limitations, both personally and as part of their helping role. Additional items about working as a team with other first responders and considering helping the person's significant others were endorsed by the local panellists. CONCLUSIONS: The study showed a high level of acceptance of the original actions suggested for inclusion in the guidelines for Australia, but also a significant number of new statements that highlight the importance of the adaptation process. Further research on the dissemination of these guidelines into a Mental Health First Aid training course for Chile and Argentina is still required.

Protein-Protein Binding Kinetics by Biolayer Interferometry.

The specific kinetics and thermodynamics of protein-protein interactions underlie the molecular mechanisms of cellular functions; hence the characterization of these interaction parameters is central to the quantitative understanding of physiological and pathological processes. Many methods have been developed to study protein-protein interactions, which differ in various features including the interaction detection principle, the sensitivity, whether the method operates in vivo, in vitro, or in silico, the temperature control, the use of labels, immobilization, the amount of sample required, the number of measurements that can be accomplished simultaneously, or the cost. Bio-Layer Interferometry (BLI) is a label-free biophysical method to measure the kinetics of protein-protein interactions. Label-free interaction assays are a broad family of methods that do not require protein modifications (other than immobilization) or labels such as fusions with fluorescent proteins or transactivating domains or chemical modifications like biotinylation or reaction with radionuclides. Besides BLI, other label-free techniques that are widely used for determining protein-protein interactions include surface plasmon resonance (SPR), thermophoresis, and isothermal titration calorimetry (ITC), among others.

Protein deuteration via algal amino acids to circumvent proton back-exchange for 1H-detected solid-state NMR.

With perdeuteration, solid-state NMR spectroscopy of large proteins suffers from incomplete amide-proton back-exchange. Using a 72 kDa micro-crystalline protein, we show that deuteration exclusively via deuterated amino acids, well-established in solution to suppress sidechain protonation without proton back-exchange obstacles, provides spectral resolution comparable to perdeuterated preparations at intermediate spinning frequencies.

Development of mental health first-aid guidelines for psychosis: a Delphi expert consensus study in Argentina and Chile.

BACKGROUND: Psychotic symptoms may be less common than anxiety or affective symptoms, but they are still frequent and typically highly debilitating. Community members can have a role in helping to identify, offer initial help and facilitate access to mental health services of individuals experiencing psychosis. Mental health first aid guidelines for helping a person experiencing psychosis have been developed for the global north. This study aimed to adapt the English- language guidelines for Chile and Argentina. METHODS: A Delphi expert consensus study was conducted with two panels of experts, one of people with lived experience of psychosis (either their own or as a carer; n = 29) and another one of health professionals (n = 29). Overall, 249 survey items from the original English guidelines and 26 items suggested by the local team formed a total of 275 that were evaluated in the first round. Participants were invited to rate how essential or important those statements were for Chile and Argentina, and encouraged to suggest new statements if necessary. These were presented in a second round. Items with 80% of endorsement by both panels were included in the guidelines for Chile and Argentina. RESULTS: Data were obtained over two survey rounds. Consensus was achieved on 244 statements, including 26 statements locally generated for the second round. Almost 20% of the English statements were not endorsed (n = 50), showing the applicability of the original guidelines but also the importance of culturally adapting them. Attributions and tasks expected to be delivered by first aiders were shrunk in favour of a greater involvement of mental health professionals. Self-help strategies were mostly not endorsed and as were items relating to respecting the person's autonomy. CONCLUSIONS: While panellists agreed that first aiders should be aware of human rights principles, items based on recovery principles were only partially endorsed. Further research on the dissemination of these guidelines and development of a Mental Health First Aid training course for Chile and Argentina is still required.

Close-Up Look at Electronic Spectroscopic Signatures of Common Pharmaceuticals in Solution.

Simulating electronic properties and spectral signals requires robust computational approaches that need tuning with the system's peculiarities. In this paper, we test implicit and fully atomistic solvation models for the calculation of UV-vis and electronic circular dichroism (ECD) spectra of two pharmaceutically relevant molecules, namely, (2S)-captopril and (S)-naproxen, dissolved in aqueous solution. Room temperature molecular dynamics simulations reveal that these two drugs establish strong contacts with the surrounding solvent molecules via hydrogen bonds. Such specific interactions, which play a major role in the spectral response and are neglected in implicit approaches, are further characterized and quantified with natural bond orbital methods. Our calculations show that simulated spectra, and especially ECD, are in good agreement with experiments solely when conformational and configurational dynamics, mutual polarization, and solute-solvent repulsion effects are considered.

Interactions and reactivity in crystalline intermediates of mechanochemical cyclorhodation reactions.

There is experimental evidence that solid mixtures of the rhodium dimer [Cp*RhCl2]2 and benzo[h] quinoline (BHQ) produce two different polymorphic molecular cocrystals called 4α and 4ß under ball milling conditions. The addition of NaOAc to the mixture leads to the formation of the rhodacycle [Cp*Rh-(BHQ)Cl], where the central Rh atom retains its tetracoordinate character. Isolate 4ß reacts with NaOAc leading to the same rhodacycle while isolate 4α does not under the same conditions. We show that the puzzling difference in reactivity between the two cocrystals can be traced back to fundamental aspects of the intermolecular interactions between the BHQ and [Cp*RhCl2]2 fragments in the crystalline environment. To support this view, we report a number of descriptors of the nature and strength of chemical bonds and intermolecular interactions in the extended solids and in a cluster model. We calculate formal quantum mechanical descriptors based on electronic structure, electron density, and binding and interaction energies including an energy decomposition analysis. Without exception, all descriptors point to 4ß being a transient structure higher in energy than 4α with larger local and global electrophilic and nucleophilic powers, a more favorable spatial and energetic distribution of the frontier orbitals, and a more fragile crystal structure.

'We see they are abandoned': Social support between people discharged from long-term psychiatric hospitalizations and their neighbors in Argentina.

BACKGROUND: Neighbors are an important component of personal social network (PSN) and despite their peripheral role and being considered as familiar strangers, they typically provide instrumental support. For people who is discharged after long-term psychiatric hospitalizations, neighbors would offer other types of social support and play a different role fostering the process of becoming full member of a given community. AIMS: To analyze the effects of neighboring on both, those who have had long-term psychiatric hospitalizations and their neighbors. METHOD: Data was collected between 2020 and 2021, including interviews with formal care staff of three housing support experiences in Argentina, and short testimonies from formerly discharged mental health service users living in the community and their neighbors. We analyzed the data using the Framework Method with a focus on the different aspects of social support and equity and reciprocity theories. RESULTS: Results suggest that emotional support was a frequent function displayed by neighbors toward people with a history of long-term psychiatric hospitalizations, which differs from typical neighboring relationships. CONCLUSIONS: Despite reciprocity was observed, users and neighbors displayed an unbalanced helping relationship.

Development of mental health first-aid guidelines for suicide risk: a Delphi expert consensus study in Argentina and Chile.

BACKGROUND: Suicide continues to pose a significant global public health challenge and ranks as one of the leading causes of death worldwide. Given the prevalence of suicide risk in the community, there is a significant likelihood of encountering individuals who may be experiencing suicidal thoughts or plans, creating an opening for non-health professionals to offer support. This study aims to culturally adapt the original Australian Mental Health First Aid Guidelines for suicide risk to the Chilean and Argentine context. METHODS: A two-round Delphi expert consensus study was conducted involving two panels, one comprising individuals with personal experience in suicide thoughts/attempts or caregiving for those with such experiences (n = 18), and the other consisting of professionals specialized in suicide assessment and support for individuals at risk (n = 25). They rated a total of 179 items mainly derived from guidelines developed by Australian experts and translated into Spanish (168), and new items included by the research team (11). The panel members were requested to assess each item utilizing a five-point Likert scale. During the second round, items that received moderate approval in the initial round were re-evaluated, and new items suggested by the local experts in the first round were also subjected to evaluation in the next round. Inclusion in the final guidelines required an 80% endorsement as "essential" or "important" from both panels. RESULTS: Consensus of approval was reached for 189 statements. Among these, 139 statements were derived from the English-language guidelines, while 50 locally generated statements were accepted during the second round. A significant difference from the original guideline was identified concerning the local experts' reluctance to discuss actions collaboratively with adolescents. Furthermore, the local experts proposed the inclusion of an entirely new section addressing suicide risk in older individuals, particularly focusing on suicide methods and warning signs. CONCLUSIONS: A Delphi expert consensus study was conducted to culturally adapt mental health first aid guidelines for assessing suicide risk in Chile and Argentina. This study involved professionals and individuals with lived experience. While many items were endorsed, some related to inquiring about suicide risk and autonomy, particularly for adolescents, were not. An additional section for older individuals was introduced. Future research should explore the implementation and impact of these adapted guidelines in training courses. This is vital for enhancing mental health support and implementing effective suicide prevention strategies in Chile and Argentina.

Paper promises: Peruvian frontline health workers' perspectives on mental health policies during COVID-19.

Governments globally deployed various non-pharmacological public health measures to respond to the COVID-19 pandemic (i.e. lockdowns and suspension of transportation, amongst others); some of these measures had an influence on society's mental health. Specific mental health policies were therefore implemented to mitigate the potential mental health impact of the pandemic. We aimed to explore the implementation of mental health regulations adopted by the Peruvian health system by focusing on the care services at Community Mental Health Centres (CMHCs), based on the experiences of health workers. We conducted a phenomenological qualitative study to understand the implementation of mental health policies launched in Peru during the COVID-19 pandemic. Data were obtained from a document review of 15 national policy measures implemented during the pandemic (March 2020 to September 2021), and 20 interviews with health workers from CMHCs (September 2021 to February 2022). The analysis was conducted using thematic content analysis. Most implemented policies adapted CMHC care services to a virtual modality during the COVID-19 pandemic; however, various challenges and barriers were evidenced in the process, which prevented effective adaptation of services. Workers perceived that ineffective telemedicine use was attributed to a gap in access to technology at the CMHCs and also by users, ranging from limited access to technological devices to a lack of technological skills. Further, although mental health promotion and prevention policies targeting the community were proposed, CMHC staff reported temporary interruption of these services during the first wave. The disparity between what is stated in the regulations and the experiences of health workers is evident. Policies that focus on mental health need to provide practical and flexible methods taking into consideration both the needs of CMHCs and socio-cultural characteristics that may affect their implementation.

Computational Insights into the Adsorption of Ligands on Gold Nanosurfaces.

We study the adsorption process of model peptides, nucleobases, and selected standard ligands on gold through the development of a computational protocol based on fully atomistic classical molecular dynamics (MD) simulations combined with umbrella sampling techniques. The specific features of the interface components, namely, the molecule, the metallic substrate, and the solvent, are taken into account through different combinations of force fields (FFs), which are found to strongly affect the results, especially changing absolute and relative adsorption free energies and trends. Overall, noncovalent interactions drive the process along the adsorption pathways. Our findings also show that a suitable choice of the FF combinations can shed light on the affinity, position, orientation, and dynamic fluctuations of the target molecule with respect to the surface. The proposed protocol may help the understanding of the adsorption process at the microscopic level and may drive the in-silico design of biosensors for detection purposes.

[Attitudes of neighbors about the treatment and community life of people with severe mental health disorders in Argentina]. / Actitudes de vecinos acerca del tratamiento y la vida en comunidad de personas con problemáticas severas de salud mental en Argentina.

A psychiatric reform is underway in Latin America and the Caribbean. Specifically in Argentina, a model of community mental health is being built, and prolonged psychiatric hospitalizations are still taking place, especially in neuropsychiatric hospitals. Therefore, it is necessary to closely monitor the psychiatric reform. One of the possible ways to monitor the reform is by analyzing society's attitudes towards prolonged psychiatric hospitalization as a mean of mental health treatment. Thus, an analytical observational study was conducted at the Buenos Aires Province, Argentina, in 2021, to analyze the behavior of neighbors of people who had prolonged psychiatric hospitalizations and who received housing support. Questionnaires were applied to neighbors and non-neighbors, addressing the behaviors toward prolonged psychiatric hospitalization as a mean of treatment, social distance toward people who were hospitalized, as well as specific interviews with key informants from neighborhoods where people with severe mental health disorders and who receive housing support live. Based on the answers of neighbors and non-neighbors, no statistically significant differences were identified in behaviors toward prolonged psychiatric hospitalization as a mean of treatment, nor for social distance in relation to people who were hospitalized. Key informants conditioned their assessment of prolonged hospitalization and valued the role of support teams in making community life viable.

La reforma psiquiátrica se encuentra en proceso en la región de América Latina y el Caribe. Específicamente en Argentina, el modelo de salud mental comunitaria está en construcción, siendo aún observable la presencia de internaciones psiquiátricas prolongadas, principalmente en hospitales neuropsiquiátricos. Resulta así necesario monitorear la reforma psiquiátrica, siendo una de las vías para ello el análisis de las actitudes de la sociedad hacia la internación psiquiátrica prolongada como modalidad de atención en salud mental. Así, se realizó un estudio observacional analítico en la Provincia de Buenos Aires, Argentina, en el año 2021, en donde se analizaron las actitudes de vecinos de personas que tuvieron internaciones psiquiátricas prolongadas y que recibían apoyos a la vivienda. Se hicieron cuestionarios a vecinos y no vecinos, indagándose por las actitudes hacia la internación psiquiátrica prolongada como modalidad de tratamiento, así como la distancia social hacia personas que tuvieron internaciones psiquiátricas, y también entrevistas a profundidad con informantes clave de barrios en donde habitan personas con problemáticas severas de salud mental y que reciben apoyos a la vivienda. No se identificaron diferencias estadísticamente significativas en las actitudes en relación a la internación psiquiátrica prolongada como modalidad de tratamiento de vecinos y no vecinos, ni tampoco respecto a la distancia social hacia personas que tuvieron internaciones psiquiátricas. Los informantes clave condicionaron su valoración sobre la internación prolongada, y valoraron el rol de los equipos de apoyo para posibilitar la vida en comunidad.

Uma reforma psiquiátrica está em curso na América Latina e Caribe. Especificamente na Argentina, um modelo de saúde mental comunitária está sendo construído, ainda acontecendo internações psiquiátricas prolongadas, principalmente em hospitais neuropsiquiátricos. Faz-se necessário, portanto, o acompanhamento da reforma psiquiátrica. Uma das formas de fazê-lo é analisando as atitudes da sociedade frente à internação psiquiátrica prolongada como forma de tratamento da saúde mental. Assim, foi realizado um estudo observacional analítico na Província de Buenos Aires, Argentina, no ano de 2021, onde foram analisadas as atitudes de vizinhos de pessoas que tiveram internações psiquiátricas prolongadas e que receberam apoio habitacional. Foram aplicados questionários a vizinhos e não vizinhos, questionando as atitudes em relação à internação psiquiátrica prolongada como forma de tratamento, bem como a distância social em relação às pessoas que foram internadas, e também entrevistas específicas com informantes-chave de bairros onde vivem pessoas com problemas graves de saúde mental e que recebem apoio habitacional. Com base nas respostas de vizinho e não vizinhos, não foram identificadas diferenças estatisticamente significantes nas atitudes em relação à internação psiquiátrica prolongada como forma de tratamento, nem em relação à distância social em relação às pessoas que foram internadas. Os informantes-chave condicionaram sua avaliação da hospitalização prolongada e valorizaram o papel das equipes de apoio na viabilização da vida comunitária.

The Role of Crystalline Intermediates in Mechanochemical Cyclorhodation Reactions Elucidated by in-Situ X-ray Powder Diffraction and Computation.

The occurrence of crystalline intermediates in mechanochemical reactions might be more widespread than previously assumed. For example, a recent study involving the acetate-assisted C-H activation of N-Heterocycles with [Cp*RhCl2 ]2 by ball milling revealed the formation of transient cocrystals between the reagents prior to the C-H activation step. However, such crystalline intermediates were only observed through stepwise intervallic ex-situ analysis, and their exact role in the C-H activation process remained unclear. In this study, we monitored the formation of discrete, stoichiometric cocrystals between benzo[h]quinoline and [Cp*RhCl2 ]2 by ball milling using in-situ synchrotron X-ray powder diffraction. This continuous analysis revealed an initial cocrystal that transformed into a second crystalline form. Computational studies showed that differences in noncovalent interactions made the [Cp*RhCl2 ]2 unit in the later-appearing cocrystal more reactive towards NaOAc. This demonstrated the advantage of cocrystal formation before the acetate-assisted metalation-deprotonation step, and how the net cooperative action of weak interactions between the reagents in mechanochemical experiments can lead to stable supramolecular assemblies, which can enhance substrate activation under ball-milling conditions. This could explain the superiority of some mechanochemical reactions, such as acetate-assisted C-H activation, compared to their solution-based counterparts.