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Complexos fosfínicos de Pd(II) com produtos naturais: síntese, caracterização, avaliação da citotoxicidade e interação com biomoléculas
(Universidade Federal de São Carlos, 2023-11-29) Dutra, Jocely de Lucena; Batista, Alzir Azevedo; https://lattes.cnpq.br/6469642481998660; https://orcid.org/0000-0002-4671-2754; https://lattes.cnpq.br/7966283355473231; https://orcid.org/0000-0002-1911-2470
This thesis details the synthesis, characterization and evaluation of antitumor activity of twelve monocationic PdII/phosphine complexes featuring ligands derived from products natural. The complexes were categorized in three Series: Series A; complexes with the general formula [Pd(cur)(P-P)]PF6, where cur=curcumin, PF6=hexafluorophosphate and P-P= PPh3=triphenylphosphine (A1), dppe=1,2-bis(diphenylphosphine)ethane (A2), dppp= 1,3-bis(diphenylphosphine)propane (A3), dppb=1,4'-bis(diphenylphosphine)butane (A4) and dppf=1,1'-bis(diphenylphosphine)ferrocene (A5); Series B, complexes with the general formula [Pd(dppe)(O-O)]PF6, where O-O= lau=lausone (B1), lap=lapachol (B2), lpm=3-styryl-lausone (B3) and ali=alizarin (B4); Series C, complexes of the type [Pd(P-P)(lap)]PF6, where P-P= dppp (C1), dppb (C2) and dppf (C3). Their characterization involves elemental analysis, molar conductivity, absorption spectroscopy in the infrared region, 1D and 2D nuclear magnetic resonance (31P{1H}, 1H and 13C{1H}), mass spectrometry and single-crystal X-ray diffraction. Stability assessment in biological relevant solvents, using UV-vis absorption spectroscopy, revealed instability on Series A, due to the self-oxidation of curcumin, as previously reported, while the Series B and C complexes were stable. The antitumor activity was evaluated in variety of cell lines, such as breast (MDA-MB-237, MCF-7 and SKBR-3), lung (A549), prostate (DU-145), ovarian (A2780 and A2780cis) and non-tumor cells of the breast (MCF-10A) and lung (MRC-5), varying the number of lines in each Series. Series A complexes showed low IC50 in several of the tumor lines tested, including some cell lines which the activity is superior to curcumin and cisplatin. The [Pd(cur)(PPh3)2]PF6 stands out in tumor lines MDA-MB-231 (5,0 ± 0,2 M), A2780 (0,5 ± 0,1 M) and A2780cis (1,4 ± 0,4 M) than the other complexes in the series, with the highest selectivity index displayed for the A2780 lineage (≥40). Series B systematically demonstrates the effects of naphthoquinones and anthraquinone coordination to Pd on IC50 values, highlighting the lapachol complex (B2) as the most active in of tumor cells tested, especially for A2780 (IC50 3.5 ± 0,1 µM, SI ≥ 11.4). In series C, C3 complex stands out presenting IC50 1.1 ± 0.2 M and SI ≥ 36.4 in A2780cis. In general, complexes A1, B2 and C3 were able to inhibit colony formation and induce morphological changes in tumor lines. Furthermore, the A1, B2, and C3 complexes promoted a cycle cell arrest in the Sub-G1 phase, which represents the fraction of dead cells with fragmented DNA. The flow cytometry assay with Annexin-V and 7-AAD showed that the complexes induce cell death by apoptosis. The complexes demonstrated weak and reversible interactions with the minor groove of DNA, without affecting its secondary and tertiary structures. Interaction assays with HSA were performed, revealing moderate to strong interactions with the complexes. The possible mechanism of death for the complexes is by inducing the formation of ROS in cells, as demonstrated for the A1 complex in A2780cis cells.
Análise de determinantes no sucesso da reorganização financeira de empresas em recuperação judicial
(Universidade Federal de São Carlos, 2023-11-29) Dias, Ana Paula Borges; Albuquerque, Andrei Aparecido de; https://lattes.cnpq.br/9667573506903226; https://orcid.org/0000-0002-2819-9993; https://lattes.cnpq.br/7038687642791910; https://orcid.org/0000-0002-2212-1108
The field of bankruptcy and insolvency is an area that is still in development, with many studies proposing new bankruptcy prediction models to bring greater accuracy to financing decisionmaking for banks and investment for shareholders. This research addresses the topic of bankruptcy and judicial recovery, and it is structured in the different articles. The first is a systematic literature review article, in which we sought to identify the evolution of the research field and its state of the art, as well as identify, through qualitative analysis, the types of models and explanatory variables most used in bankruptcy prediction. The main results in this article were that the most commonly used model for bankruptcy prediction in the analyzed studies was Altman's Z-Score; the most used variables are profitability, liquidity, and debt ratio; and the most common types of models were logistic regression and multivariate discriminant analysis. The research continues with the second article, which is a quantitative study applying Z-Score models to Brazilian samples, aiming to analyze both the models' performance and the variables. For this article, it was found that the Altman models did not perform as well in the selected sample as they did in the sample for which they were developed, achieving a 10% Type I error and a 33% Type II error for the Revised Z-Score model, and a 52% Type I error and a 3% Type II error for the Emerging Markets model. However, based on the results of the F-tests applied to the Z-Score models' variables, they have significant discriminant abilities for the bankruptcy and judicial recovery event. The third and final article is the development of an emergency or judicial recovery prediction model, which, unlike most existing studies in the field, does not aim to identify when a company will become insolvent or bankrupt, but rather to identify among those in this state which are capable of recovering. In this work, the proposed model achieved an AUC of 95.74, a 17% Type I error, and a 4% Type II error. For practical purposes, this research provides relevant information for decision-making by managers and investors, not only for bankruptcy but also for corporate recovery and emergence, and identifies significant variables for this event.
Sífilis gestacional e congênita: análise epidemiológica antes e após a implementação de uma política pública para o controle da sífilis congênita em Iguatu – Ceará/Brasil
(Universidade Federal de São Carlos, 2023-11-29) Albuquerque, Fideralina Rodrigues de; Souto, Bernardino Geraldo Alves; https://lattes.cnpq.br/7264826508407685; https://orcid.org/0000-0003-4083-3050; Padilha, Roberto de Queiroz; https://lattes.cnpq.br/2262980850254605; https://lattes.cnpq.br/6220335601593014; https://orcid.org/0000-0003-0567-4381
Syphilis is considered a sexually transmitted infection that, when not treated early and adequately, can develop into a chronic illness. Faced with the problem of Syphilis, the municipality of Iguatu-CE was one of the two municipalities in Ceará benefiting from the “Projeto Carta Acordo OPAS” which aimed to reduce the incidence rate of congenital Syphilis. The municipality's participation promoted changes in the way of tackling the syphilis problem, in which a series of recommendations were adopted, constituting a municipal public policy. As objectives, we attempted to carry out an epidemiological analysis of cases of gestational and congenital syphilis in the municipality of Iguatu-CE from May 2019 to April 2023, emphasizing the repercussions that occurred after the implementation of public policy in the municipality. As method, as method, we got information from gestational and congenital syphilis notification forms, made available by the Notifiable Diseases Information System – SINAN, was used. The data were disaggregated into periods, the first being from May 2019 to April 2021 (closing date of the training provided by the Project and beginning of actions implemented by the municipality) and the second between May 2021 to April 2023. The epidemiological description was carried out based on global descriptive statistics, as well as comparative and correlation analyze between the two periods. 83 new cases were reported throughout the period, 71 cases of gestational syphilis and 12 of congenital syphilis. There was an increase in notifications of cases of gestational syphilis and a 50% reduction in cases of congenital syphilis after the public policy. The highest prevalence occurred in young, black and mixed-race women with low education. Clinically, an improvement in indicators is observed after the implementation of public policy, such as a greater proportion of diagnoses confirmed in the first trimester of pregnancy and a greater proportion of treatments carried out appropriately. Concluding, the reduction in underreporting of gestational syphilis and vertical transmission of syphilis are associated with the implemented municipal public policy. Thus, as the changes implemented by the Department of Health present a low cost for the municipality, it is recommended that this public policy be extended to other municipalities in the State of Ceará, encouraging actions such as improving the testing, monitoring and treatment processes offered in Basic Health Care, in addition to allowing the prescription and administration of Benzantine Penicillin to be carried out by trained nurses. As in other evidence, the cases of gestational and congenital syphilis in the municipality of Iguatu-CE point to problems of inequity in access to health, mainly affecting pregnant women in situations of social vulnerability, making it necessary to broaden the perspective and care in relation to women in this social extract.
Exploring the potential of blockchain for traceability in supply chain: a hybrid simulation approach
(Universidade Federal de São Carlos, 2023-11-29) Risso, Lucas Antonio; Santa-Eulalia, Luis Antonio de; https://lattes.cnpq.br/9501843917802087; https://orcid.org/0000-0002-7246-8230; Ganga, Gilberto Miller Devós; https://lattes.cnpq.br/9062191157466610; https://orcid.org/0000-0001-9328-5727; https://lattes.cnpq.br/6340394387734472; https://orcid.org/0000-0003-3461-4804
While the scientific literature on blockchain applications in supply chain management is vast, it is short of empirical evidence due to the novelty of the technology and the inherent complexity of implementing such systems. In situations where empirical evidence is lacking or difficult to gather, modeling and simulation serve as effective tools for capturing the complexities of supply chain networks. This allows for a thorough examination and understanding of these systems, facilitating informed and consistent decision-making. Consequently, potential advantages and risks can be identified prior to their implementation in the real world. However, guidelines to assist scholars and practitioners in creating realistic hybrid simulation models in this context are missing in the literature, which brings great complexity to the modeling process. Thus, the main objective of this work is to propose and test a framework to support the modeling and simulation of supply chain traceability considering blockchain technology. The framework comprises a step-by-step guide that embraces the phases of model design, model development, and output evaluation. In addition, to enhance understanding and adoption, this research incorporates concepts and terminologies from existing and well-established frameworks for both practitioners and scholars, namely SCOR, GTS, and ADACOR. Furthermore, it employs a hybrid modeling approach that combines principles and methods from agent-based modeling and discrete-event simulation paradigms. To accomplish this objective, this work is deployed in three parts. First, to deal with a large publication rate of works related to blockchain in supply chain management, a review of reviews is developed, which is a tertiary study that gathers evidence from literature reviews. Secondly, following the Design Science Research approach, a novel methodological framework is proposed to help build hybrid simulation models of different levels of granularity. Finally, to demonstrate its potential, the proposed methodological framework is applied to a real-scale industrial case in Canada, comprising a live lobster supply chain to identify the potential impacts of a blockchain-based traceability system on the physical supply chain network structure through the lens of network theory, considering single and multi-level supplier evaluation.
Sistema Integrado de Respostas Técnicas - SIRT: trajetória, papel institucional e desafios contemporâneos
(Universidade Federal de São Carlos, 2023-11-29) Carvalho, Beatriz Leal de; Fonseca, Sérgio Azevedo; https://lattes.cnpq.br/2879240108726907; https://orcid.org/0000-0002-8457-2668; https://lattes.cnpq.br/2764605945358954; https://orcid.org/0000-0002-0338-1465
SBRT is especially developed for micro and small companies – MPEs, legally constituted, and that demanded technical solutions. Its objective is to facilitate rapid access to low-complexity technological solutions in specific areas, in addition to promoting the dissemination of knowledge and contributing to the technology transfer process, especially for smaller companies (RAMOS et al., 2006). To meet the objectives set, the SBRT was created as a network made up of nine technical response agents, with “specialists from institutions with recognized performance in innovation and technology, which prepare quick answers to the most diverse technical questions free of charge” (SBRT, 2023). One of the executing agents of this network is the Integrated System of Technical Responses, linked to the Universidade Estadual Paulista Júlio de Mesquita Filho (SIRT/UNESP), the object of study on this research. The SIRT has not yet been the subject of more in-depth investigation. Therefore, this can be treated as a justification for carrying out this research, which was guided by the following question: what are the institutional and operational characteristics of the SIRT and its historical contributions as an agent of technical responses to the SBRT? The main objective of the research is to evaluate the impacts of SIRT as a manager of knowledge and low-complexity innovations in the period between 2010 and 2023. To achieve this objective, the research covered the following specific objectives: i) map and record the historical evolution and structural (agents) and operational (products) changes in SIRT; ii) analyze local impacts regarding the university-governmentbusiness relationship and iii) characterize the results generated in knowledge management for SBRT. To achieve the proposed objectives, a qualitative approach was chosen from a historical, exploratory and descriptive perspective, framed as a single case study, adopting documentary research as the main data collection instrument. For data processing, document analysis was defined. Regarding the results, focused on the trajectory, institutional role and contemporary challenges of the SIRT, it was found that it presented positive results, fulfilling the objectives initially outlined in terms of knowledge management. Furthermore, among the positive results it is important to consider the intense development of the university tripod of teaching, research and extension, developed over the years of SIRT operation. In addition to this, it is also necessary to consider the contribution of SIRT to the effectiveness of the triple helix in the joint action of UNESP, the State, municipal entities and MSEs. It is also necessary to emphasize that data control, document gaps, the lack of situational analysis and the absence of indicators are weak points in the operationalization of the service and that deserve attention not only from the SIRT, but also from the SBRT Network. Furthermore, for effective intellectual, social and economic development to be possible, effective support from the State is essential. This is because, as presented in this research, the integral development of Brazil, whether due to its productive characteristics, territorial size or the needs resulting from these factors, urgently demands the prioritization of MSEs and the establishment of solid cooperation networks that consider all agents social.