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Adição de espécies radicalares a azometinas iminas e nitronas: síntese e aplicação de c-glicosil pirazolidinona e obtenção de aminas via LMCT
(Universidade Federal de São Carlos, 2025-08-05) Gonçalves, Renan de Oliveira; Paixão, Márcio Weber; https://lattes.cnpq.br/3773908504964104; https://orcid.org/0000-0002-0421-2831; https://lattes.cnpq.br/5141145224355244; https://orcid.org/0000-0003-2061-8628; Assis, Francisco Fávaro de; Pastre, Julio Cezar; Raminelli, Cristiano; Lüdtke, Diogo Seibert; https://lattes.cnpq.br/0182263452298453; https://lattes.cnpq.br/2428327858391101; https://lattes.cnpq.br/3153931165773039; https://lattes.cnpq.br/0831151849844477; https://orcid.org/0000-0002-2042-8915; https://orcid.org/0000-0001-9972-425X; https://orcid.org/0000-0002-6920-5456; https://orcid.org/0000-0002-9135-4298
Nitrogen compounds play a central role in several areas of applied chemistry, being present in agrochemicals, pharmaceuticals, food additives, and polymeric materials. Among the modern strategies for obtaining and modifying these structures, methodologies based on photocatalysis stand out, allowing the selective generation of radicals under visible light. In this context, this thesis describes the development of innovative synthetic approaches for the functionalization of nitrogenous species such as azomethine imines and nitrones, exploiting their capacity as nucleophilic radical acceptors in photoinduced reactions. In Project 1, a metal-free photocatalytic methodology was developed for the non-anomeric C-glycosylation of azomethine imines, using 4-glycosyl-1,4-dihydropyridines (DHPs) as radicais precursors and 4CzIPN as a photocatalyst in acetonitrile. The protocol resulted in the development of a new class of C-glycosyl pyrazolidinones under mild conditions, with broad scope and scalability. The derivatives obtained were subsequently modified, including acylation, acetonide deprotection, and reduction, demonstrating the synthetic potential of the methodology. Furthermore, the C-glycosylation methodology was adapted to continuous flow systems, enabling the efficient synthesis of a library of 30 compounds with greater savings in time, reagents, and solvents. The products obtained were subjected to antiplasmodial activity assays in collaboration with CIBFar-USP. Sixteen compounds demonstrated significant activity (IC50 < 10 µM) with low cytotoxicity and good selectivity. Structure-activity relationship analysis revealed that the presence of a phenyl at position 5 of the pyrazolidinone and the glycosidic moiety are determinants of bioactivity, consolidating these units as promising pharmacophoric fragments against Plasmodium falciparum. In Project 2, a novel strategy was developed for the alkylation of nitrones and subsequent reduction of hydroxylamine to amines using ligand-to-metal charge transfer (LMCT) catalysis with Fe(III) under visible light. The methodology employs carboxylic acids as a source of alkyl radicals and initially generates hydroxylamines in situ, which are reduced to amines without the use of stoichiometric metal reducing agents. Overall, the results obtained throughout this thesis demonstrate the potential of photochemical approaches in the development of sustainable and efficient methodologies for the selective functionalization of nitrogenous systems, in addition to contributing new perspectives for the discovery of bioactive compounds.
Avançando a estimação robusta e confiável de efeitos de tratamento heterogêneos: inovações metodológicas e avaliações críticas
(Universidade Federal de São Carlos, 2025-08-05) Souto, Hugo Gobato; Louzada Neto, Francisco; https://lattes.cnpq.br/0994050156415890; https://lattes.cnpq.br/6289579571895447; https://orcid.org/0000-0002-7039-0572
Context: The robust and reliable estimation of Heterogeneous Treatment Effects (HTEs) is crucial across many scientific disciplines, yet it faces significant methodological challenges including model complexity, confounding, computational burden, and rigorous evaluation practices. Objectives: This thesis aimed to advance the field of HTE estimation by developing and critically evaluating methodologies that enhance the rigor, efficiency, and practical utility of causal inference techniques. Methodological Contributions: The work presents three primary contributions: (1) An empirical validation of the importance of ablation studies for complex nonparametric causal models, specifically examining the Bayesian Causal Forest (BCF) and the role of its propensity score component; (2) The development of the Test-Informed Simulation Count Algorithm (TISCA), a principled approach for determining the necessary number of replications in simulation studies for model evaluation using statistical principles; and (3) The introduction of the Differencein-Differences Bayesian Causal Forest (DiD-BCF), a novel non-parametric estimator for robust causal inference in DiD settings, particularly effectively addressing treatment effect heterogeneity through a Parallel Trends Assumption (PTA)-based reparameterization. Principal Findings: Ablation studies revealed that the propensity score component in BCF is not essential for performance and its omission can reduce computation time by approximately 21%. TISCA was shown to provide statistically justified simulation counts, promoting efficiency and enhancing the credibility of comparative model evaluations. DiDBCF demonstrated considerably superior performance over established benchmarks and uncovering nuanced conditional treatment effects in an empirical application to U.S. minimum wage policy. Overall Conclusion and Implications: This thesis collectively champions a paradigm of increased rigor, efficiency, and nuanced understanding in HTE estimation. It provides researchers with critically evaluated insights and novel tools— ablation study advocacy, a statistically grounded simulation design algorithm, and an advanced non-parametric DiD estimator—to generate more robust, reliable, and actionable causal evidence, thereby strengthening the foundation for evidence-based decision-making across various disciplines.
Responsividade e responsabilidade no presidencialismo brasileiro: 1995 a 2022
(Universidade Federal de São Carlos, 2025-08-05) Gregorio, Paulo Cesar dos Santos; Ribeiro, Pedro José Floriano; https://lattes.cnpq.br/6336151484882362; https://orcid.org/0000-0001-8669-5795; https://lattes.cnpq.br/2129229489875840; https://orcid.org/0000-0002-2901-1067; Diniz, Simone; Tarouco, Gabriela da Silva; Silva, Mariana Batista da; Casalecchi, Gabriel Ávila; https://lattes.cnpq.br/9726360676770459; https://lattes.cnpq.br/3456458764216995; https://lattes.cnpq.br/5144800413272494; https://lattes.cnpq.br/9759794253878555
Assuming the premise that political parties expected to implement in government, at least partially, the policies advocated during the electoral campaigns, this dissertation aims to assess the effects of coalition's composition and presidential term length on governing party’s capacity to accommodate the structural tension between responsiveness and responsibility in Brazil. The investigation covers the period from 1995 to 2022, encompassing the administrations of Fernando Henrique Cardoso, Luiz Inácio Lula da Silva, Dilma Rousseff, Michel Temer, and Jair Bolsonaro. A mixed-methods approach is employed, combining qualitative content analysis of party manifestos and televised campaign broadcasts (Horário Gratuito de Propaganda Eleitoral – HGPE) with statistical modeling via Negative Binomial Regression (NB), suitable for discrete and overdispersal data. Six econometric models were estimated: two focusing on the overall frequency of responsive and responsible actions, and four addressing the specific subdimensions of responsibility – namely, social, international, fiscal-political, and other categories. The empirical findings reveal convergent patterns between responsiveness and responsibility, highlighting three key results: (1) presidents serving their first term are less likely to issue normatively justified actions in either dimension, suggesting a pattern of strategic caution; (2) greater coalition cohesion is systematically associated with lower levels of normative production in both dimensions, indicating that more stable arrangements prioritize institutional maintenance over programmatic innovation; and (3) ideological heterogeneity within the governing coalition exerts a positive effect on the volume of justified actions, supporting the hypothesis that plural coalitions require increased normative legitimation efforts by the Executive. These findings suggest that presidential behavior is not solely driven by ideological orientation or public pressure, but rather emerges from a complex institutional architecture involving programmatic bargaining, coordination costs, and adaptive strategies of governance within multiparty contexts.
Formação continuada e adaptações curriculares na escola do/no campo: percepção dos professores dos anos iniciais do ensino fundamental
(Universidade Federal de São Carlos, 2025-08-05) Mota, Luciene Sandes; Pinheiro, Rosa Aparecida; https://lattes.cnpq.br/6292207464385037; https://orcid.org/0000-0002-4910-4842; https://lattes.cnpq.br/4033363551135499; https://orcid.org/0009-0002-0571-3416; Cruz, Divoene Pereira; Sant'Ana, Izabella Mendes; https://lattes.cnpq.br/5450633055305958; https://lattes.cnpq.br/7860235863062183
The dissertation Continuing Education and Curriculum Adaptations in Rural Schools: Teachers’ Perceptions in the Early Years of Elementary Education presents the results of a study conducted with teachers working from the 1st to the 5th grade of elementary school. The research was carried out in a municipal institution located in the rural area of Porto Feliz, in the interior of São Paulo state, with the participation of five teachers. A quantitative-qualitative approach was adopted, combining elements of both methodologies to provide a more comprehensive analysis of the phenomenon under investigation. The central aim was to investigate teachers’ perceptions of continuing education and curriculum adaptations implemented to meet the specificities of rural education. The study sought to answer the following question: What are the perceptions of teachers working in the early years of elementary education in a public school located in the rural area of Porto Feliz regarding continuing education and the curriculum adaptations made to address the particularities of rural education? The specific objectives included understanding how continuing education takes place for teachers working in rural schools, focusing on their own perceptions; identifying the need for curriculum adaptations that take into account the unique characteristics of these institutions; and analyzing how the particularities of rural life are perceived and integrated both into the curriculum and into teacher education. The instruments for data collection included: a literature review on Rural Education and continuing teacher education; a questionnaire to obtain preliminary information about participants’ training; narrative interviews; and document analysis. The research findings reveal that the school curriculum is predominantly limited to modifications made by teachers, based on the official curriculum guidelines of the Municipal Department of Education. There is a noticeable lack of opportunities for the effective integration of themes that foster socio-educational practices, which could enhance the value of the traditional knowledge of rural families and their ways of life. In addition, no continuing education programs tailored to the specific needs of teachers working in this context were identified. This scenario highlights a pedagogical organization in rural schools that diverges from the formative demands required to respect local identities. By analyzing the perspectives of teachers in a rural school in Porto Feliz on their professional development and curriculum adaptations, this study provides insights to improve pedagogical practices and to formulate educational public policies that are better suited to the needs of the rural context. By valuing teachers’ experiences as a source of knowledge, it contributes to building a more just and inclusive rural education.
Estudo da fotoinativação de larvas de Aedes aegypti (LINNAEUS, 1762) com formulações de curcumina: eficácia e segurança ambiental
(Universidade Federal de São Carlos, 2025-08-05) Garbuio, Matheus; Lima, Alessandra Ramos; https://lattes.cnpq.br/2937413804518289; https://orcid.org/0000-0001-5810-5137; Bagnato, Vanderlei Salvador; https://lattes.cnpq.br/4947860249518663; https://orcid.org/0000-0003-4833-239X; https://lattes.cnpq.br/4970296342450124; https://orcid.org/0000-0001-9055-205X; Lacava, Paulo Teixeira; Caires, Anderson Rodrigues Lima; Postacchini, Bruna Bueno; Godoi, Lívia Mara Alves Figueiredo; https://lattes.cnpq.br/8947678349043750; https://lattes.cnpq.br/4615245702160544; https://lattes.cnpq.br/6705532687184556; https://lattes.cnpq.br/7061694896531030; https://orcid.org/0000-0001-7166-606X; https://orcid.org/0000-0002-2602-9480; https://orcid.org/0000-0002-4606-8604; https://orcid.org/0000-0002-6690-9650
The selection of resistant populations of the vector Aedes aegypti to traditional chemical insecticides has motivated the search for alternative techniques to control the proliferation of vector mosquitoes. Photodynamic inactivation (PDI) is a promising tool against vector Ae. aegypti, involving the combination of three elements: specific wavelength, photosensitive molecule (PS) and molecular oxygen, which when associated cause irreversible damage. Ambient temperature is an important factor in the survival of larvae and mosquitoes, as it influences their physiology, behavior and ecology. This study aimed to evaluate curcumin-based formulations for PDI of Ae. aegypti larvae under laboratory and simulated field conditions. The implementation was carried out in stages: (i) the biological cycle parameters of Ae. aegypti, such as hatching rate and lethal concentration (LC) of larvae and mortality promoted by PDI with curcumin, under different temperatures (20, 25, 30 and 35 °C). (ii) formulation and characterization of microencapsulated curcumin by ultraviolet-visible (UV-Vis) absorption spectroscopy, scanning electron microscopy (SEM), confocal microscopy, and Fourier transform infrared spectroscopy (FTIR), and biological assays with larvae. Lethal concentrations (LCs50;90) for IFD action in the laboratory were defined. (iii) evaluation of the photodynamic action behavior in a simulated field, based on the LCs determined in the laboratory, evaluated larval mortality and the persistence of the curcumin-based formulation. (iv) ecotoxicological analyses with non-target organisms (Danio rerio, Allium cepa, and Galleria mellonella). The results of step i) indicated that higher temperatures result in higher larval mortality at lower concentrations of the curcumin formulation. The larvae that survived after PDI, when compared to the control groups, showed delayed development. The survival evaluation of adult male and female mosquitoes for the control and PDI groups showed a reduction in the longevity of mosquitoes in the PDI group compared to the control. In step ii), the curcumin microcapsule presented an absorption peak at 440 nm, an average size of 11.1 ± 3.1 µm, and there were no significant shifts in the positions of the characteristic bands of curcumin and its excipients. Furthermore, it maintained its efficacy, and laboratory results show that the LCs were 0.27 mg/L (LC50) and 1.6 mg/L (LC90), respectively. Step (iii), in a simulated field, the concentrations obtained were LC50 2.30 mg/L and LC90 8.7 mg/L, respectively. The results of the persistence evaluation of the curcumin microcapsule in a simulated field showed 100% efficacy for up to 20 days, with activity declining over time, completely losing its efficacy after 45 days. In stage IV, the ecotoxicity evaluation showed no toxicity to non-target organisms: Danio rerio (100 mg/L), Allium cepa (100 mg/L) and Galleria mellonella (2000 mg/L). The photodynamic action is effective in laboratory and simulated field tests. Therefore, the curcumin-based photolarvicide may be a potential integrated control agent for the Ae. aegypti vector in the larval stage and, consequently, for reducing arbovirus transmission.
O projeto de vida no ensino de filosofia e o direcionamento profissional dos jovens no ensino médio
(Universidade Federal de São Carlos, 2025-08-05) Falasqui, Raquel Aparecida; Maamari, Adriana Mattar; https://lattes.cnpq.br/5707827597161294; https://lattes.cnpq.br/0562415581840634; Silva, Jefferson Luis Brentini da; Queiroz, Rouseane da Silva Paula; https://lattes.cnpq.br/8964083164248988; https://lattes.cnpq.br/4041714082174829
This study analyzed the importance of Philosophy for the career choices of public high school students in Campinas, São Paulo, through its integration with the Life Project course and the development of philosophical workshops. The research was motivated by gaps observed in preparing students to identify their vocations and define their professional futures. It sought to understand how Philosophy offers perspectives on professional choice, going beyond the mere selection of careers and enabling young people to reflect on their paths and goals, while emphasizing the contribution of this field of knowledge to articulating aptitude, values, and professional decisions. The partnership between Philosophy and Life Project contributed to the development of students’ autonomy, broadening reflections of a personal, community, and professional nature. This articulation proved essential for shaping students who are better prepared to recognize their principles, face life’s challenges, and understand the demands of the labor market. In this context, the research designed and implemented a Philosophy workshop focused on professional orientation, aiming to support young people at the end of high school and to encourage dialogue and authorship in building their trajectories. To develop the workshop, a qualitative action research methodology was adopted, allowing an understanding of students’ experiences through the analysis of activities carried out and their prior knowledge. The workshop fostered the integration of Philosophy and Life Project through exploratory practices, such as ethical and environmental dilemmas related to real-life situations. The role of the teacher as a learning guide was crucial for carrying out the activities and for fostering reflection and student protagonism. Based on attentive observation, student feedback, interviews, and the analysis of records, the study demonstrated the contribution of Philosophy to the development of skills and to understanding the professional world, moving beyond strictly academic content. Interaction with professionals from different fields and practical activities helped young people gain a clearer understanding of their career options, aligning their personal choices with labor market demands. The proposal encouraged a renewed view of themselves, reinforcing the value of their choices and broadening their vision of their future professional trajectories.