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N1-acetyl-N2-formyl-5-methoxykynuramine (AFMK) is one of the primary oxidation products of melatonin. There is growing evidence of its beneficial biological properties, including antioxidant features and modulators of cytokines and enzymes involved in the inflammatory process. Here, the autoxidation of melatonin mediated by UVC was studied regarding the formation of AFMK and the reaction mechanism. The parameters evaluated were irradiation, pH, dissolved oxygen, superoxide radical anion, and hydroxyl radical. We found that the AFMK yield is directly correlated with UVC irradiation. The AFMK concentration decreased 95% when a 280 nm cutoff filter blocked the irradiation. By removing the dissolved oxygen from the medium, the decrease was 90%. Superoxide dismutase, acting as a scavenger of superoxide radical anion, caused a 64% reduction. At pH 7.0, the AFMK yield was just 14% of those obtained at pH 10. These findings are consistent with a typical autoxidation reaction. In addition, the low yield of AFMK in the absence of UVC irradiation suggested that electronically excited melatonin is the species involved in the initial electron transfer. Density Functional Theory (DFT) calculations were performed to strengthen the proposal. Corroborant with the experimental results, the theoretical analyses revealed that electron transfer from melatonin to molecular oxygen is only energetically feasible in the excited state. In conclusion, the direct autoxidation of melatonin at excited state in alkaline pH is a straightforward approach to producing AFMK.

Objective: In recent years, emotion regulation strategies such as cognitive reappraisal (CR) and expressive suppression (ES) have emerged as potential transdiagnostic mechanisms of change. Functional models of emotion dysregulation hypothesize that avoidance strategies like ES maintain internalizing distress symptoms, but these models have not received close empirical scrutiny in treatment studies. The objective of this study was to test whether week-to-week within-person changes in CR and ES predicted changes in negative affect (NA) and positive affect (PA) in a guided self-help intervention. Methods: N = 141 participants were recruited for a six-week remote trial of a guided self-help transdiagnostic CBT (NCT04870099). NA was measured with the Kessler Scale Psychological Distress Scale (K6) and PA with the World Health Organization-5 Well-being Index (WHO-5). We used the Emotion Regulation Questionnaire (ERQ) to measure CR and ES and disaggregated within- versus between-person variability using a random intercept cross-lagged panel model. Results: Participants (Mage = 40.36, SDage = 13.95, nfemale = 120, nnon-Hispanic white = 110) improved in NA, PA, CR, and ES across the trial, with the smallest improvements in ES. At the between-person level, CR was associated with both NA (r = -0.22, p = .022) and PA (r = 0.40, p < .001). At the within-person level, week-to-week changes in CR were associated with subsequent week-to-week decreases in NA (ranging from β = -0.28 to β = -0.55). Conclusions: Our findings support the role of cognitive restructuring as a mechanism of change in transdiagnostic CBT.

Made available in DSpace on 2022-05-01T08:44:40Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-08-20 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Vegetable oil has been widely used to synthesize monomers and polymers in different fields. Some authors have found different polymers in maleinized vegetable oil; however, they have not described the luminescent properties of the polymers in an intensive way. This work aimed to synthesize new polymers from macadamia oil using diethylene glycol and glycerol as crosslinkers and their characterization The results obtained by spectroscopic analyses confirmed the incorporation of anhydride, as well as the reactions for the final polymers. Results from UV-Vis showed that maleinized macadamia oil presented an aggregation-induced emission effect with solvatochromic effect with absorption at 201.6 nm (ethanol) and 241.8 nm (chloroform), which was corroborated by theoretical calculations. Moreover, the luminescent property exhibited by both obtained polymers was kept even after the swelling test, and powdering the samples. Therefore, these polymers, synthetized in a fast way and without catalyst, open a new field of renewable and sustainable materials with luminescent properties that can be applied in technological fields, such as solar cells and fluorescent sensors. School of Sciences Department of Chemistry UNESP- São Paulo State University Institute of Chemistry Department of Physical Chemistry UNICAMP-Campinas State University Campinas School of Sciences Department of Chemistry UNESP- São Paulo State University CAPES: 011/2009 CAPES: 024/2012

There is a growing interest in developing scalable interventions, including internet-based cognitive-behavioral therapy (iCBT), to meet the increasing demand for mental health services. Given the growth in diversity worldwide, it is essential that the clinical trials of iCBT for depression include diverse samples or, at the very least, report information on the racial-ethnic composition of their samples. Unfortunately, the field lacks data on how well racial-ethnic diversity is currently reported and represented in the iCBT literature. Therefore, we conducted a systematic review to examine the overall reporting of racial and ethnic identities in published clinical trials of iCBT for depression. We also reviewed the representation of specific racial and ethnic minority groups. We used a database of randomized controlled trials focusing on iCBT studies. A total of 62 iCBT randomized control trials and 17,210 participants are summarized in this study. Only 27.4% of the trials reported race, and only 17.7% reported ethnicity. Reporting outside of the United States (U.S.) was very poor, with the U.S. accounting for 88.2% of studies that reported race and 81.8% for ethnicity. Within and without the United States, the most reported race was White (74.9%), followed by Black (7.5%), and Asian (5.7%). Furthermore, when translating this to individual participants, 13,587 (78.9%) participants had no reported race, and 14,810 (86.0%) had no reported ethnicity. These findings suggest that reporting on race-ethnicity is very poor outside the U.S. Furthermore, while studies in the U.S. tend to report on racial-ethnic representation, the representation itself is quite poor.

Digital, El presente trabajo de investigación tiene como objetivo principal el desarrollo de las competencias digitales en la I.E Rural Samaná del municipio de San Carlos – Antioquia, debido a que la aparición del covid-19, trajo consigo la virtualidad en el aprendizaje, lo que termino de poner en evidencia las dificultades que se presentaban en esta escuela rural, en el manejo de competencias digitales y TICS. Es importante resaltar que la institución educativa se ubica en un territorio que fue epicentro del conflicto armado en Colombia, donde la gran mayoría de los pobladores son víctimas de la violencia que azoto al país durante más de 50 años. Otro factor a tener en cuenta, son las desigualdades existentes entre el campo y la ciudad, sobre todo en temas educativos, por eso la relevancia y pertinencia del trabajo de grado. El proyecto se desarrolla con la aplicación de un instrumento propuesto por el centro de aprendizaje virtual de la universidad de Santander, es un instrumento diagnostico que busca evaluar el estado actual del uso de las competencias digitales por parte de algunos docentes de la institución educativa. Los resultados de la prueba diagnóstica evidenciaron las falencias en que se encuentran los docentes de esta institución en el uso de las TICS y de las competencias digitales, seguidamente se inicia con las capacitaciones para los docentes a través de dos seminarios-taller, donde se empieza a evidenciar un reconocimiento y desarrollo de algunas competencias digitales por parte de los docentes de la I.E Rural Samaná., The main objective of this research work is the development of digital skills in the Samaná Rural I.E. of the municipality of San Carlos – Antioquia, due to the appearance of covid-19, it brought virtuality into the classrooms, which ended up highlighting the difficulties that arose in this rural school, in the management of digital skills and ICTs. It is important to note that the educational institution is located in a territory that was one of the epicenters of the armed conflict in Colombia, where the vast majority of the residents are victims of the violence that plagued the country for many years. Another factor to take into account is the abysmal inequalities that exist between the countryside and the city, especially in educational matters, hence the relevance of the degree work. The project is developed with the application of an instrument proposed by the virtual learning center of the University of Santander, it is a diagnostic instrument that seeks to evaluate the current state of the use of digital skills by some teachers of the educational institution. The results of the diagnostic test evidenced the shortcomings in which the teachers of this institution find themselves in the use of ICTs and digital skills, then it begins with the training for teachers through two seminar-workshops, where it begins to evidence a recognition and development of some digital skills by the teachers of the IE Rural Samaná., Maestría, Magíster en Tecnologías Digitales Aplicadas a la Educación, 1°ed, CONTENIDO Pág INTRODUCCIÓN..................................................................................................15 1. PRESENTACIÓN DEL TRABAJO DE GRADO ..............................................16 1.1 PLANTEAMIENTO DEL PROBLEMA ................................................17 1.2 ALCANCE..........................................................................................22 1.3 JUSTIFICACIÓN................................................................................22 1.4 Objetivos............................................................................................26 1.4.1 Objetivo general ................................................................................26 1.4.2 Objetivos específicos ........................................................................26 2 BASES TEÓRICAS........................................................................................27 2.1 ESTADO DEL ARTE..........................................................................27 2.2 MARCO REFERENCIAL....................................................................33 2.2.1 Marco Teórico ...................................................................................33 2.2.2 Marco Conceptual .............................................................................35 3 DISEÑO METODOLÓGICO ...........................................................................37 3.1 TIPO DE INVESTIGACIÓN................................................................37 3.2 HIPÓTESIS........................................................................................38 3.3 VARIABLES O CATEGORÍAS...........................................................38 3.4 OPERACIONALIZACIÓN DE VARIABLES O DESCRIPCIÓN DE CATEGORÍAS................................................................................................39 3.5 POBLACIÓN Y MUESTRA ................................................................39 3.6 PROCEDIMIENTO.............................................................................40 3.7 INSTRUMENTOS DE RECOLECCIÓN DE INFORMACIÓN .............42 3.8 TÉCNICAS DE ANÁLISIS DE DATOS...............................................42 4 CONSIDERACIONES ÉTICAS.......................................................................43 5 DIAGNÓSTICO INICIAL.................................................................................45 INSTRUMENTO PROYECTO DE EVALUACIÓN DE COMPETENCIAS -............47 6 estructura de la propuesta de intervención .....................................................59 6.1 PROPUESTA PEDAGÓGICA............................................................59 6.1.1. PLAN DE FORMACION DOCENTE .....................................................61 6.2 TALLER 1 Y 2....................................................................................62 6.3 COMPONENTE TECNOLÓGICO......................................................64 6.4 IMPLEMENTACIÓN...........................................................................65 7 ANÁLISIS E INTERPRETACIÓN DE DATOS ................................................66 8 CONCLUSIONES...........................................................................................72 9 LIMITACIONES..............................................................................................75 10 IMPACTO / recomendaciones / TRABAJOS FUTUROS.............................76 11 Bibliografía..................................................................................................79 ANEXOS ..............................................................................................................83

BACKGROUND Self-help interventions have the potential to increase access to evidence-based mental health care. Self-help can be delivered via different formats, including print media or digital mental health interventions (DMHIs). However, we do not know which delivery format is more likely to result in higher engagement. OBJECTIVE The aims of this study were to identify if there is a preference for engaging in print media vs. DMHIs and whether there are individual differences in relative preferences. METHODS Participants were 423 adults between the ages of 18 and 82 years old (48% female) recruited on Prolific to be a nationally representative sample of the US population (Non-Hispanic White=69%, Non-Hispanic Black=12%, Asian 7.3%, Hispanic=5.9%, Other=5.2%). We provided individuals with psychoeducation on different self-help formats and measured their willingness to use print media vs. DMHIs. We also measured participants’ demographics, personality, and perception of each format’s availability and helpfulness and used these to predict individual differences in the relative preferences. RESULTS Participants reported being more willing to engage with print media than DMHIs (B=.41, SE=.08, t=4.91, P CONCLUSIONS This study suggests an overall preference for print media over DMHIs. Future work should study whether receiving mental health treatment via participants’ preferred delivery format can lead to higher engagement.

Made available in DSpace on 2021-06-25T10:25:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 Singlet oxygen (1O2) is the “active principle” in photodynamic therapy. Taurine chloramine (Tau-NHCl) and hydrogen peroxide (H2O2) are well-tolerated and widely used antiseptics. Due to its mild oxidizing features and stability, Tau-NHCl can be directly used to treat skin diseases. We found that a diluted aqueous mixture of Tau-NHCl and H2O2 acts as a slow and long-lasting potential source of 1O2. The reactions were studied by luminol-enhanced chemiluminescence. Evidence of the formation of 1O2 was obtained using deuterium oxide, sodium azide and 9,10-Anthracenediyl-bis(methylene)dimalonic acid, a chemical trap of 1O2. The reaction was optimized, and a mechanism was proposed, including theoretical calculations at B3LYP/6-311++G(3df,2p) level of theory, adding D3Bj empirical dispersion and SMD (Water) solvent effects. Chloramines produced by the reactions between HOCl and L-alanine, 3-amino-1-propanesulfonic acid and gamma-aminobutyric acid were also prepared, and their reactivity and stability were compared with Tau-NHCl. We found that Tau-NHCl is more stable and adequate for the production of 1O2. In conclusion, we propose applying these drugs combination as a potential source of 1O2 with applications for skin diseases treatment. Department of Chemistry Faculty of Sciences UNESP - São Paulo State University Department of Physical Chemistry Institute of Chemistry Campinas State University (UNICAMP) Department of Chemistry Faculty of Sciences UNESP - São Paulo State University

Cognitive-behavioral therapies (CBTs) are the most widely studied form of psychotherapy for disorders like depression and anxiety. Nonetheless, there is heterogeneity in response to CBTs vs. other treatments. Researchers have become increasingly interested in using pre-treatment individual differences (i.e., moderators) to match patients to the most effective treatments for them. Several methods to combine multiple variables to create precision treatment rules (PTRs) that identify subgroups have been proposed. We review the rationale behind multivariable PTRs as well as the findings of studies that have used different PTRs. We identify conceptual and methodological issues in the literature. Multivariable treatment assignment is a promising avenue of research. Nonetheless, effect sizes appear to be small and most of the samples that have been used to study these questions have been grossly underpowered to detect small effects. We recommend researchers explore multivariable treatment selection strategies, particularly those resembling risk stratification, in heterogeneous samples of patients undergoing low-intensity CBTs vs. realistic minimal controls.

Os conceitos referentes à mecânica quântica são de suma importância para o estudo da estrutura do átomo. A investigação desses conceitos e de como eles são estruturados pelo estudante de Química têm adquirido relevância nas pesquisas de ensino de Química, sobretudo pelas dificuldades de aprendizagem dos entes submicroscópicos em relação aos macroscópicos. Nessa perspectiva, a presente pesquisa tem por foco apresentar uma proposta analítica da aprendizagem dos estudantes de Química no estudo dos conceitos do modelo atômico atual, em especial os números quânticos, formas dos orbitais e transições eletrônicas, com base na Teoria da Ação Mediada. A investigação foi realizada na disciplina de Química Geral II do curso de Química da Universidade Federal do Maranhão-UFMA, e constitui-se como parte dos resultados de uma pesquisa de doutorado. A proposta analítica da aprendizagem foi dividida em três momentos: mapa de aulas, mapa de categorias e microanálise. Esta analisou a interação dos alunos-agindo-com-as-ferramentas-socioculturais, como os Objetos de Aprendizagem, e o modo como produziram os significados dos conceitos, permitindo ter uma visão detalhada do processo de aprendizagem e que a inserção de ferramentas socioculturais favorecem o rol apreciativo dos alunos na significação dos conceitos e influenciam o discurso de autoridade durante as interações comunicativas. Palavras-chave: Teoria da Ação Mediada. Modelo Atômico Quântico. Produção de Significados. Objetos de Aprendizagem. The production of meaning in the quantum model through sociocultural tools: an analytical proposal of learning Abstract The concepts related to quantum mechanics are of utmost importance for the study of the atom structure. The investigation of these concepts and how they are structured by the Chemistry student has acquired relevance in the research of the subject’s teaching, especially by the learning difficulties of submicroscopic entities in relation to macroscopic ones. From this perspective, this research focuses on presenting an analytical proposal of the learning of Chemistry students in the study of the concepts of the current atomic model, especially quantum numbers, orbital forms and electronic transitions based on the Theory of Mediated Action. The research was carried out during General Chemistry II classes of the Chemistry course of the Federal University of Maranhão-UFMA, and is part of the results of a doctoral research. The analytical proposal of learning was divided into three moments: class map, category map and microanalysis. It analyzed the interaction of the students acting with sociocultural tools, such as the Learning Objects and the way they produced the meanings of the concepts, allowing a detailed view of the learning process and that of the insertion of socio-cultural tools favors the appreciative role of the students in the meaning of the concepts and influences the authority word during the communicative interactions. Keywords: Mediated Action Theory. Quantum Atomic Model. Production of Meanings. Learning Objects.

This work aims to produce and disseminate videos that follow the microlearning methodology, to explain the physicochemical properties of cobalt (II) chloride hexahydrate through thermal analysis, and to determine the reliability of the Portuguese good luck rooster. Temporal and social accelerations due to the growth of the technological world are changing the old teaching-learning methodologies; thus, new methods should be explored. In the microlearning methodology, short segments and specific content can be broadcast to anyone at any time. In addition, relating new information to individual’s experiences can favor the teaching-learning process. The good luck rooster is an ornament of Portuguese origin, which can forecast the weather in a limited way, and is composed of cobalt (II) chloride hexahydrate. This compound was characterized by TG-DTA (Simultaneous Thermogravimetry-Differential Thermal Analysis) and DSC (Differential Scanning Calorimetry), verifying that the salt loses its hydration water when exposed to high temperatures, changing its color from pink color to blue.

Este artigo constituiu-se como um recorte do projeto de pesquisa intitulado “A Robótica, o Pensamento Computacional e as Tecnologias Digitais na Educação Básica: Potencializando Aprendizagens e Competências em Processos de Ressignificação do Ensino de Ciências”, em desenvolvimento desde novembro de 2019, com o financiamento do Conselho Nacional de Desenvolvimento Científico e Tecnológico – CNPq, Ministério da Ciência, Tecnologia, Inovações e Comunicações – MCTI, a partir da Chamada Universal MCTIC/CNPq – Edital nº 05/2019 – Programa Ciência na Escola – Ensino de Ciências na Educação Básica, com o apoio da Universidade Nove de Julho-Uninove/SP-Brasil. Neste artigo são apresentados exemplos das experiências desenvolvidas e os resultados alcançados, a partir da percepção dos jovens participantes deste projeto no segundo semestre de 2021, a fim de elucidar as contribuições de um “Clube de Ciências e Tecnologias Interescolar” para ações de internacionalização, a partir da parceria entre universidade e instituições escolares de diferentes países (Brasil e Equador) envolvidas nessa investigação.

Introduction: Doing What Matters in Times of Stress (DWM) is a five-module transdiagnostic guided self-help (GSH) intervention developed by the World Health Organization, originally in a group-based format. In a sample of individuals recruited from across the United States, we conducted an open trial to study the feasibility and acceptability of an adaptation of DWM in which guidance was provided individually and remotely via phone and videoconferencing. Methods: We assessed internalizing symptoms, psychological well-being, work and social functioning, usability of the intervention, and emotion regulation over the course of six weeks. Results: A total of 263 individuals completed our screening. Of those, 75.29% (n = 198) qualified for the intervention. We reached most participants who qualified (71.21%, n = 141) via phone to schedule a GSH session. Most of those scheduled attended a study session (84.4%, n = 119), and most of those who attended a session completed more than half the treatment (84.03%, n = 100). Retention rates were comparable to meta-analytic estimates of dropout rates in GSH. Participants showed improvement on internalizing symptoms, psychological well-being, work and social functioning, usability of the intervention, and emotion regulation. Conclusion: DWM is a freely available, seemingly efficacious transdiagnostic intervention for internalizing disorder symptoms.

A análise complexa é, na atualidade, um objeto matemático fundamental, tendo em vista sua aplicabilidade às mais variadas áreas da Ciência. Este trabalho propõe mais um entrelaçamento interessante desse conteúdo matemático com as Artes Visuais, através da computação gráfica. A apresentação de padrões estéticos, utilizando o método domain coloring para a visualização de uma função complexa, mostra que propriedades algébricas e geométricas podem ser “coloridas”, o que torna o seu estudo mais humano, contextualizado, agradável e dinâmico, possibilitando maior capacidade de entendimento, absorção e, até mesmo, de criação de conceitos. Este trabalho evidencia, mais uma vez, a contribuição da interdisciplinaridade ao estudo da Matemática.

Neste artigo apresentamos um trabalho desenvolvido com licenciandos calouros em Matemática, no qual, buscou-se a produção de significados através do desenvolvimento de uma sequência didática proposta utilizando o software GeoGebra, visando a análise do nível de domínio e de apropriação dos conceitos de funções polinomiais de uma variável real. A análise dos dados coletados está fundamentada na teoria da ação mediada de James Wertsch, a qual tem como foco o estudo sociocultural da mente e a memória coletiva sobre os aspectos históricos mediados pelas ferramentas culturais concernentes às instituições formais de ensino. O público alvo consistiu em nove (9) estudantes, sendo cinco (5) do sexo masculino e quatro (4) do sexo feminino, do curso de Licenciatura em Matemática da Universidade Estadual Paulista - UNESP, em Bauru, São Paulo, Brasil. A pesquisa, de caráter qualitativo, pode ser caracterizada como um estudo de caso, visto que envolveu a busca por significados atribuídos aos sujeitos da pesquisa relativos às suas vivências e experiências pessoais. As atividades desenvolvidas com o software de geometria dinâmica e as reflexões solicitadas na sequência didática contribuíram para a experimentação, a criação de estratégias, a produção de conjecturas, a argumentação qualitativa e a dedução de propriedades matemáticas relativas aos conteúdos destas funções de uma variável real. Os licenciandos com maior base teórica em Matemática foram capazes de explorar os recursos computacionais com maior destreza, acuidade e precisão, conseguindo assim, maior aprofundamento nos conteúdos por eles explorados. Esses alunos apresentaram, ainda, um detalhamento com bom nível de rigor matemático em suas explicações sobre os conteúdos abordados, cometendo poucos erros de notação simbólica.

Technological advances stimulate an increasingly globalized and virtually interconnected society, making the exploitation of technology resources in the area of education no longer the object of discussion, but of reflection. Several software with interactive proposals are developed daily, arousing the curiosity of students in digital interaction. Obtaining good results using these tools is an object of concern for teachers and the school community. Thus, in order to understand how mathematical experiments occur with the use of dynamic geometry software, especially GeoGebra, in basic education, we present in this article a bibliographic survey of works on this theme. Most of the studies analyzed focused on geometry content. Among the results, the following stand out: the good reflection provoked by the activities, the formulation of hypothesis and conjectures, in addition to arousing the arguments in students. These notes are important, as they demonstrate that these experimental activities using the GeoGebra software underpin and drive the learning of Mathematics in a dynamic way and meet the contemporary demands of modern society, training the student in the field of technologies.

A sociedade do século XXI incorpora a cada dia novas ferramentas tecnológicas aos seus afazeres o que acarreta alterações no comportamento e no modo de vida da população. Neste contexto, o aprendizado de linguagens de programação pode favorecer o raciocínio lógico e o Pensamento Computacional, além de capacitar o estudante, oferecendo um conhecimento mais amplo das áreas tecnológicas. A presente pesquisa discute o Pensamento Computacional e averigua as habilidades do Pensamento Computacional nas produções de licenciandos. A análise das propostas de abordagem indicou que dos 07 grupos participantes, apenas 03 previram ações para o desenvolvimento das principais habilidades do Pensamento Computacional.Palavras Chave: Ensino de Matemática. Pensamento Computacional. Geometria. Habilidades.

Made available in DSpace on 2022-04-29T08:30:38Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-08-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) UGC-DAE Consortium for Scientific Research, University Grants Commission The crescent evolution of a global pandemic COVID-19 and its respiratory syndrome (SARS-Cov-2) has been a constant concern (Ghosh 2021; Khan et al. 2021; Alazmi and Motwalli 2020; Vargas et al. 2020). The absence of a proven and effective medication has compelled all the scientific community to search for a new drug. The use of known drugs is a faster way to develop new therapies. Molecular docking is a powerful tool (Gao et al. J Mol Model 10: 44–54, 2004; Singh et al. J Mol Model 18: 39–51, 2012; Schulz-Gasch and Stahl J Mol Model 9:47–57, 2003) to study the interaction of potential drugs with SARS-CoV-2, Alsalme et al. (2020) and Sanders et al. (2020) spike protein as a consequence the main goal of this article is to present the result of the study of an interaction between (R and S)-Linezolid with receptor-binding domain (RBD) of SARS-Cov-2 spike protein complexed with human Angiostensin-converting enzyme 2 (ACE2) (6vW1 - from PDB). The Linezolid enantiomers were optimized at B3LYP/6-311++G(2d,p) level of theory. Molecular docking of the system (S)-Linezolid⋯RBD⋯ACE2 and (R)-Linezolid⋯RBD⋯ACE2 was performed, the analysis was made using LigPlot+ and NCIplot software packages, to understand the intermolecular interactions. The UV-Vis and ECD of the complexes - (R and S)-Linezolid⋯RBD⋯ACE2 were performed in two layers with DFT/6-311++G(3df,2p) and DFT/6-31G(d), respectively. The results showed that only the (S)-Linezolid had a stable interaction with − 8.05 kcal.mol− 1, whereas all the R-enantiomeric configurations had positive values of binding energy. The (S)-Linezolid had the same interactions as in the (S)-Linezolid ⋯ Haluarcula morismortui Ribosomal system, where it is well-known the fact that the latter has biological activity. A specific interaction on the fluorine ring justified an attenuation on the ECD signal, in comparison to isolated species. Therefore, some biological activity of (S)-Linezolid with SARS-CoV-2 RBD was expected, indicated by the modification of its ECD signal and justified by a similar interaction in the S-Linezolid⋯Haluarcula marismortui Ribosomal system. Department of Physical Chemistry Campinas State University Institute of Chemistry, Campinas School of Science Department of Chemistry São Paulo State University, Bauru Department of Chemistry University of Calcutta, 92, A.P.C. Road School of Science Department of Chemistry São Paulo State University, Bauru FAPESP: 2013/08293-7 FAPESP: 2015/22338-9 CNPq: 303581/2018-2 CNPq: 305541/2017- 0 UGC-DAE Consortium for Scientific Research, University Grants Commission: 4-5/2018

Made available in DSpace on 2019-10-04T12:38:15Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-09-15 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The solvent-induced Stokes' shift, which describes the response at different solvents (acetonitrile, chloroform, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, ethanol, heptanol, tetrahydrofuran, and toluene) to a sudden change in the charge distribution of excited 4-(Dicyanomethylene)-2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) molecule, was studied through absorption and emission spectra and TD-DFT calculations; the solvent effect was studied trough the IEF-PCM model. The application of IEF-PCM model with TD-DFT methods to obtain the absorption energies provided excellent match with the experimental results. The results observed, for solvents effects on the positions of maxima absorption and emission between experimental data and theoretical calculations, have average absolute deviations of only 0.03 eV and 0.22 eV, respectively. A systematic error was observed by comparing the theoretical and experimental maxima for the emission energies. However, the application of the Lippert-Mataga and Bilot-Kawski equations to the TD-DFT-simulated Stokes' shifts values resulted in excellent correlation coefficients: Lippert-Mataga, R-2 = 0.9982, Bilot-Kawski, R-2 = 0.9908 and R-2 = 0.9795. (C) 2019 Elsevier B.V. All rights reserved. Univ Estadual Campinas, UNICAMP, Inst Chem, Dept Phys Chem, BR-13083861 Campinas, SP, Brazil Sao Paulo State Univ, UNESP, Fac Sci, Dept Chem, BR-17033360 Bauru, SP, Brazil Sao Paulo State Univ, UNESP, Fac Sci, Dept Chem, BR-17033360 Bauru, SP, Brazil FAPESP: 2016/20549-5 FAPESP: 2015/22338-9 FAPESP: 308480/2016-3 FAPESP: 2016/04963-6 FAPESP: INCT.Bio.Nat 2014/50926-0 CNPq: 302793/2016-0 CNPq: 306975/2013-0 CNPq: 305541/2017-0 CNPq: 440503/2014-0

Made available in DSpace on 2019-10-06T17:14:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-01-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Vanillic acid is a widely used food additive (flavouring agent, JECFA number: 959) with many reported beneficial biological effects. The same is true for its ester derivative (methyl vanillate, JECFA number: 159). Based on the increasing evidence that diapocynin, the dimer of apocynin (NADPH oxidase inhibitor), has some improved pharmacological properties compared to its monomer, here the dimer of methyl vanillate (MV), i.e., methyl divanillate (dimer of methyl vanillate, DMV) was synthesized and studied in the context of its redox properties and binding affinity with human serum albumin (HSA). We found that the antioxidant potency of DMV was significantly increased compared to MV. In this regard, the reduction of 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical by DMV was 30-fold more effective compared to MV. Ferric ion reduction was 4-fold higher and peroxyl radical reduction was 2.7-fold higher. The interaction with HSA was significantly improved (Stern-Vomer constants, 3.8 × 105 mol-1 L and 2.3 × 104 mol-1 L, for DMV and MV, respectively). The complexation between DMV and HSA was also evidenced by induced circular dichroism (ICD) signal generation in the former due to its fixation in the asymmetric protein pocket. Density-functional calculations (TD-DFT) showed that the ICD spectrum was related to a DMV conformation bearing a dihedral angle of approximately -60°. Similar dihedral angles were obtained in the lowest and most populated DMV cluster poses obtained by molecular docking simulations. The computational studies and experimental displacement studies revealed that DMV binds preferentially at site I. In conclusion, besides being a powerful antioxidant, DMV is also a strong ligand of HSA. This is the first study on the chemical and biophysical properties of DMV, a compound with potential beneficial biological effects. Department of Chemistry Faculty of Sciences UNESP-São Paulo State University Laboratory of Computational Biology and Bioinformatics UFABC-Federal University of ABC Department of Physical Chemistry Institute of Chemistry Campinas State University (UNICAMP) Department of Chemistry Faculty of Sciences UNESP-São Paulo State University FAPESP: 2014/50926-0 FAPESP: 2016/20549-5 FAPESP: 2016/22014-1 CNPq: 302793/2016-0 CNPq: 305541/2017-0