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      Analysis of the autopsy, toxicological, and psychiatric reports of Portugal’s first major forensic case: part III


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          This work presents an odd historical record obtained through more than 14 years of research regarding one of the first major European forensic cases. The presumed homicide of Mário Guilherme Augusto de Sampaio in 1890 was allegedly perpetrated by his uncle, the prestigious doctor Vicente Urbino de Freitas. This famous poisoning had international repercussions for decades, with the participation of several forensic experts that made the history of forensic sciences, namely forensic toxicology and pathology. This third work aims to collect, restore, and analyse all the forensic evidence, particularly from the autopsy, toxicological, and psychiatric forensic reports. Facts regarding the life of Vicente Urbino de Freitas during his exile in Brazil were also recovered, along with a vast and outstanding assortment of forensic medicine photographs from the 19th century.

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          Most cited references41

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          Alkaloids fromDelphiniumstaphisagria

          Three new diterpenoid alkaloids, isoazitine (1), 19-oxodihydroatisine (2), and 22-O-acetyl-19-oxodihydroatisine (3), and eight known alkaloids-azitine (4), dihydroatisine (5), delphinine, neoline, bullatine C (14-acetylneoline), chasmanine, 14-acetylchasmanine, and the quaternary base atisinium chloride (7)-were isolated from the aerial parts of Delphinium staphisagria. Structures of the new alkaloids were established mainly by 1D and 2D NMR spectroscopy, including (1)H COSY, HMQC, HMBC, and ROESY. The (1)H and (13)C NMR data for alkaloids 4 and 5 are also reported.
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            The effect of diphenylhydantoin (Dilantin) sodium on atrial flutter and fibrillation provoked by focal application of a conitine or delphinine.

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              Aconitum and Delphinium sp. alkaloids as antagonist modulators of voltage-gated Na+ channels. AM1/DFT electronic structure investigations and QSAR studies.

              Early pharmacological studies of Aconitum and Delphinium sp. alkaloids suggested that these neurotoxins act at site 2 of voltage-gated Na(+) channel and allosterically modulate its function. Understanding structural requirements for these compounds to exhibit binding activity at voltage-gated Na(+) channel has been important in various fields. This paper reports quantum-chemical studies and quantitative structure-activity relationships (QSARs) based on a total of 65 natural alkaloids from two plant species, which includes both blockers and openers of sodium ion channel. A series of 18 antagonist alkaloids (9 blockers and 9 openers) have been studied using AM1 and DFT computational methods in order to reveal their structure-activity (structure-toxicity) relationship at electronic level. An examination of frontier orbitals obtained for ground and protonated forms of the compounds revealed that HOMOs and LUMOs were mainly represented by nitrogen atom and benzyl/benzoylester orbitals with -OH and -OCOCH(3) contributions. The results obtained from this research have confirmed the experimental findings suggesting that neurotoxins acting at type 2 receptor site of voltage-dependent sodium channel are activators and blockers with common structural features and differ only in efficacy. The energetic tendency of HOMO-LUMO energy gap can probably distinguish activators and blockers that have been observed. Genetic Algorithm with Multiple Linear Regression Analysis (GA-MLRA) technique was also applied for the generation of three-descriptor QSAR models for the set of 65 blockers. Additionally to the computational studies, the HOMO-LUMO gap descriptor in each obtained QSAR model has confirmed the crucial role of charge transfer in receptor-ligand interactions. A number of other descriptors such as logP, I(BEG), nNH2, nHDon, nCO have been selected as complementary ones to LUMO and their role in activity alteration has also been discussed.

                Author and article information

                Forensic Sci Res
                Forensic Sci Res
                Forensic Sciences Research
                Taylor & Francis
                7 May 2021
                7 May 2021
                : 6
                : 3 , Special Issue on Sharing clinical and forensic toxicology knowledge in the era of a pandemic and beyond; Guest editor: Nikolas P. Lemos
                : 250-272
                [a ]Department of Public Health and Forensic Sciences, and Medical Education, Faculty of Medicine, University of Porto , Porto, Portugal
                [b ]IINFACTS—Institute of Research and Advanced Training in Health Sciences and Technologies, Department of Sciences, University Institute of Health Sciences (IUCS), Advanced Polytechnic and University Cooperative (CESPU), CRL , Gandra, Portugal
                [c ]UCIBIO-REQUIMTE, Laboratory of Toxicology, Department of Biological Sciences, Faculty of Pharmacy, University of Porto , Porto, Portugal
                Author notes
                CONTACT Ricardo Jorge Dinis-Oliveira ricardinis@ 123456sapo.pt ; ricardinis@ 123456med.up.pt
                Author information
                © 2021 The Author(s). Published by Taylor & Francis Group on behalf of the Academy of Forensic Science.

                This is an Open Access article distributed under the terms of the Creative Commons Attribution License ( http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                Page count
                Figures: 21, Tables: 5, Pages: 23, Words: 11121

                forensic sciences,forensic reports,alkaloids,history of legal medicine,flores street,vicente urbino de freitas,josé antónio de sampaio junior,mário guilherme augusto de sampaio


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