Experimental micromorphology in Tierra del Fuego (Argentina): building a reference collection for the study of shell middens in cold climates

Commonly used in archaeological contexts, micromorphology did not see a parallel advance in the field of experimental archaeology. Drawing from early work conducted in the 1990`s on ethnohistoric sites in the Beagle Channel, we analyze a set of 25 thin sections taken from control features and experimental tests. The control features include animal pathways and environmental contexts (beach samples, forest litter, soils from the proximities of archaeological sites), while the experimental samples comprise anthropic structures, such as hearths, and valves of Mytilus edulis (the most important component of shell middens in the region) heated from 200 degrees C to 800 degrees C. Their micromorphological study constitutes a modern analogue to assist archaeologists studying site formation and ethnographical settings in cold climates, with particular emphasis on shell midden contexts. (c) 2010 Elsevier Ltd. All rights reserved.

Computer-aided Structure Elucidation of Neolignans

This paper describes a new module of the expert system SISTEMAT used for the prediction of the skeletons of neolignans by (13)C NMR, (1)H NMR and botanical data obtained from the literature. SISTEMAT is composed of MACRONO, SISCONST, C13MACH, H1MACH and SISOCBOT programs, each analyzing data of the neolignan in question to predict the carbon skeleton of the compound. From these results, the global probability is computed and the most probable skeleton predicted. SISTEMAT predicted the skeletons of 75% of the 20 neolignans tested, in a rapid and simple procedure demonstrating its advantage for the structural elucidation of new compounds.

New Improvements in Automatic Structure Elucidation Using the LSD (Logic for Structure Determination) and the SISTEMAT Expert Systems

This article describes the integration of the LSD (Logic for Structure Determination) and SISTEMAT expert systems that were both designed for the computer-assisted structure elucidation of small organic molecules. A first step has been achieved towards the linking of the SISTEMAT database with the LSD structure generator. The skeletal descriptions found by the SISTEMAT programs are now easily transferred to LSD as substructural constraints. Examples of the synergy between these expert systems are given for recently reported natural products.

C-glycosyl flavones from Peperomia blanda

The methanol extract from aerial parts of the Peperomia blanda (Piperaceae) yielded two C-glycosyl-flavones. Their structures were elucidated on the basis of extensive spectroscopic analysis, including 1D and 2D NMR, chemical transformation and comparison with the related known compounds. The structure of the new flavonoids were established as 4`-methoxy-vitexin 7-O-beta-D-xylopyranoside (1) (7-O-beta-D-xylopyranosyl-8-C-beta-D-glucopyranosyl-4`-methoxy-apigenin) and vicenin-2 (2). The antioxidant activity of both compounds was investigated using the DPPH assay. Both compounds showed only modest activity, with IC50 values of 357.2 mu M for 1, and 90.5 mu M for 2. (C) 2008 Elsevier B.V. All rights reserved.

Use of self-organizing maps and molecular descriptors to predict the cytotoxic activity of sesquiterpene lactones

Some sesquiterpene lactones (SLs) are the active compounds of a great number of traditionally medicinal plants from the Asteraceae family and possess considerable cytotoxic activity. Several studies in vitro have shown the inhibitory activity against cells derived from human carcinoma of the nasopharynx (KB). Chemical studies showed that the cytotoxic activity is due to the reaction of alpha,beta-unsaturated carbonyl structures of the SLs with thiols, such as cysteine. These studies support the view that SLs inhibit tumour growth by selective alkylation of growth-regulatory biological macromolecules, such as key enzymes, which control cell division, thereby inhibiting a variety of cellular functions, which directs the cells into apoptosis. In this study we investigated a set of 55 different sesquiterpene lactones, represented by 5 skeletons (22 germacranolides, 6 elemanolides, 2 eudesmanolides, 16 guaianolides and nor-derivatives and 9 pseudoguaianolides), in respect to their cytotoxic properties. The experimental results and 3D molecular descriptors were submitted to Kohonen self-organizing map (SOM) to classify (training set) and predict (test set) the cytotoxic activity. From the obtained results, it was concluded that only the geometrical descriptors showed satisfactory values. The Kohonen map obtained after training set using 25 geometrical descriptors shows a very significant match, mainly among the inactive compounds (similar to 84%). Analyzing both groups, the percentage seen is high (83%). The test set shows the highest match, where 89% of the substances had their cytotoxic activity correctly predicted. From these results, important properties for the inhibition potency are discussed for the whole dataset and for subsets of the different structural skeletons. (C) 2008 Elsevier Masson SAS. All rights reserved.

Computer-Assisted Approach to Structural Elucidation of Lignans

This paper reports an expert system (SISTEMAT) developed for structural determination of diverse chemical classes of natural products, including lignans, based mainly on 13C NMR and 1H NMR data of these compounds. The system is composed of five programs that analyze specific data of a lignan and shows a skeleton probability for the compound. At the end of analyses, the results are grouped, the global probability is computed, and the most probable skeleton is exhibited to the user. SISTEMAT was able to properly predict the skeletons of 80% of the 30 lignans tested, demonstrating its advantage during the structural elucidation course in a short period of time.

A general survey and some taxonomic implications of diterpenes in the Asteraceae

This paper provides a general survey of the occurrence of diterpenes in the Asteraceae. Data on 4351 botanical occurrences were obtained from the literature. These were grouped by skeleton for each genus. Then, the genera were grouped by subtribes, which, in turn, were gathered in tribes, followed by subfamilies. In spite of the low number of species containing diterpenes, it was possible to describe some structural features of these compounds, i.e. The skeletal types in various taxa and the positions in some skeletons that are always oxidized or never undergo oxidation in some genera. Thus, it was verified that: in the subfamily Cichorioideae, only a few of the studied species possess diterpenes, wherein kaurane is the most frequent diterpene skeleton. In the Asteroideae, the presence of diterpenes is much greater than that in the Cichorioideae and Carduoideae. At tribal taxonomic level, for example, the Astereae produce labdanes and clerodanes; Heliantheae and Eupatorieae produce kauranes and labdanes, respectively; and Calenduleae produce pimaranes. Some taxonomic implications are presented. (c) 2005 the Linnean Society of London.

Triterpenes from Maytenus macrocarpa and evaluation of their anti-HIV activity

A set of pentacyclic triterpenes has been isolated from the bark of Maytenus macrocarpa (Celastraceae). It includes two new olean-12-ene derivatives, namely 3 beta, 22(alpha-dihydroxy-olean-12-en-30-oic acid (1) and 22 alpha-hydroxy-olean-12-en-3-oxo-30-oic acid (2), and the new urs-12-ene derivative 3-(E)-coumaroyluvaol (7), along with 10 known compounds possessing olean-12ene, urs-12-ene, lupane and friedelane skeletons. The structures have been elucidated by extensive spectroscopic methods including ID- and 2D-NMR experiments, as well as ESI-MS analysis. All isolated compounds were tested for anti-HIV activity in C8166 cells infected with HIV-1(MN), the most active compound was 22(alpha-hydroxy-12-en-3-oxo-29-oic acid (triterpenonic acid A, 4), with an EC50 value of I mu g/mL and a selectivity index of 35.

A program for terpenoid skeleton prediction based on botanical information

This paper describes a new program developed to the SISTEMAT expert system, the SISOCBOT program. This program employs the botanical data analysis and predicts, at the end of analysis, the probable skeleton of a compound based on the input of family or genus names. The SISOCBOT program was tested with 78 samples involving 302 substances, pertaining to 38 carbon skeletons, and showed a high hit index on skeleton prediction, thus emphasizing the potential importance of these data for structural determination of natural products. © 2002 Elsevier Science Ltd. All rights reserved.

Registro de dinossauros na região da cidade de Coroatá, EO/Mesoalbiano da Bacia de São Luís-Grajaú, Estado do Maranhão

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Revisão taxonômica do gênero Hassar Eigenmann & Eigenmann, 1888, com a descrição osteológica de Hassar orestis (Steindachner, 1875) (Siluriformes, Doradidae)

O gênero Hassar (Doradidae) é um grupo natural de Siluriformes Neotropical. No presente trabalho foi realizada revisão taxonômica do referido gênero com a descrição osteológica de Hassar orestis, espécie-tipo do gênero. Este estudo foi fundamentado no levantamento e análise de caracteres morfológicos, morfométricos, merísticos e de padrão de coloração para o reconhecimento das espécies válidas e conseqüentes diagnoses e redescrições. Foram analisados 727 exemplares, provenientes de instituições nacionais e estrangeiras, envolvendo indivíduos preservados em álcool, preparados para esqueleto seco, diafanizados, radiografados e fotografados. Os exemplares foram analisados diretamente ou com auxílio de microscópio-estereoscópico e câmara clara. Medidas foram feitas, preferencialmente, do lado esquerdo do indivíduo. A descrição osteológica de Hassar orestis foi fundamentada na análise de 23 exemplares de instituições nacionais e estrangeiras e foi dividida em grupos funcionais osteológicos que são: elementos do neurocrânio, arco mandibular, arco hióide, arcos branquiais, esqueleto axial, placas nucais e nadadeira dorsal, sistema látero-sensorial e esqueleto apendicular. Os dados foram digitalizados e armazenados em formato de planilhas. Os resultados mostraram que Hassar é formado por duas espécies válidas: H. orestis e H. affinis. Hassar orestis é a espécie-tipo, tendo como sinônimo H. ucayalensis. Hassar affinis tem como sinônimos H. wilderi, H. iheringi e H. woodi. Hassar orestis e H. affinis se diferenciam pela posição do 1° espinho medial (no escudo infranucal ou entre o 1° e 8° escudo lateral vs. entre o 9° e 16° escudo lateral), número de escudos laterais providos de espinho medial (24 a 33 vs. 18 a 23) e pelos divertículos marginais filiformes da bexiga natatória (distintamente maiores vs. reduzidos ou ausentes). Os adultos (> 14 cm) de H. orestis e H. affinis diferiram pela altura do pedúnculo caudal (4,11-5,71% SL vs. 5,73 -7,63% SL) e pelo tamanho da pálpebra adiposa (conspícua e alongada na borda anterior dos olhos vs. tênue na borda anterior dos olhos). Não houve diferenças morfológicas, morfométricas e merísticas entre jovens e adultos da mesma espécie. As espécies apresentaram o mesmo padrão de coloração. Exemplares de H. orestis (N=551) possuem mancha enegrecida subterminal nos primeiros raios da nadadeira dorsal, diferentemente de H. affinis (N=176) cuja mancha pode ser subterminal ou terminal. A presença de prolongamento cartilaginoso no primeiro raio da nadadeira dorsal, em alguns machos de H. orestis, corroborou o dimorfismo sexual para espécie. Exemplares de H. orestis, provenientes dos rios Amazonas, Solimões e Negro, diferem da população do rio Branco e das Bacias dos rios Essequibo e Orinoco pela presença ou não de espinhos nos escudos timpânicos e no escudo infranucal. Não há diferença quanto à bexiga natatória dessas populações. A distribuição de H. affinis foi ampliada para os rios Solimões, Tapajós, baixo e alto Xingu, Tocantins, Araguaia, Parnaíba e Sistema Pindaré-Mearim. Hassar affinis e H. orestis apresentam ampla distribuição, parcialmente disjunta, com uma área de simpatria. A descrição osteológica da espécie-tipo proporcionou um melhor conhecimento anatômico do grupo, que serve de dado básico para trabalhos como anatomia, ontogenia, ecomorfologia e futuros eventuais trabalhos de sistemática e taxonomia.

Estudo do mecanismo do nitrofeniletano na prostaglandina-endoperóxido sintase e relação estrutura-propriedade de nitroderivados

Estudos anteriores sugerem que o óleo essencial da Aniba canelilla contendo altos níveis de 1-nitro-2-feniletano apresenta atividade antinociceptiva, antiinflamatória e hipotensora. Um estudo teórico de correlação entre estrutura química versus atividade biológica do 1-nitro-2-feniletano e a prostaglandinaendoperóxido sintase foi realizado. Além disso, foi feita uma análise conformacional do nitrofeniletano, bem como modificações em sua estrutura química, obtendo-se derivados nitroestirenos e cinamatos, para a posterior avaliação da relação estrutura-propriedade. A análise conformacional do nitrofeniletano foi realizada usando o método DFT/B3LYP com o conjunto de base 6-31G(d) através da variação da torção do angulo dihedro entre as ligações dos carbonos C₁-C₂ ligadas aos grupos fenila e nitro, com variação de intervalos de 5°, na faixa de 0° a 180°, visando a busca dos confôrmeros de menor energia. O confôrmero de 180º do dihedro O₂N-C₁-C₂-C₆H₅ foi significativamente mais estável e isto pode ser explicado em termos do equilíbrio pela presença de sete geometrias de mais baixas energias. A análise de HOMO e LUMO mostra que os grupamentos fenila e metileno contribuem para a formação deste orbital. O cálculo de energia e determinação de propriedades eletrônicas relacionadas com o mecanismo de interação com a ciclooxigenase demonstrou boa correlação entre os grupos nitro e carboxílico, os quais podem ser classificados como bioisósteros. Os resultados das propriedades físico-químicas calculadas indicam uma maior correlação do nitrofeniletano com o ácido acetilsalicílico, podendo ter seu mecanismo de ação relacionado através de interações com a Arg-120 e Ser-530.Cálculos realizados com a guanidina protonada pelo DFT/B3LYP/6-31G(d,p) parao complexo contendo o grupo carboxilato exibem uma energia de interação mais favorável, com valor de -136,34 kcal/mol, quando comparado com a molécula contendo o grupo nitro, com valor de -12,84 kcal/mol, o que pode explicar a maior efetividade da indometacina, semelhante aos resultados biológicos. Os derivados do nitrofeniletano apresentaram uma relação estrutural com derivados de cinamatos, diferindo nas propriedades redox, o que pode favorecer o desenvolvimento de estruturas protótipo como moléculas bioativas a partir destes esqueletos moleculares.

Estimativa da altura por dimensões dentárias: uma revisão da literatura

The knowledge of Forensic Anthropology is very importance in cases of identification of human remains. One phase of this process is the study of human height, which can be accomplished with relative ease when intact corpses, complete skeletons or long bones are available. However, the experience of Forensic Dentistry is essential in situations in which there is only information of the skull or of the teeth. The objective of this study was to review in the literature and evaluate works concerning the estimate of the height calculated from dental dimensions. Carrea, in 1920, proposed the estimation of the probable height of an individual by developing formulas for maximum and minimum heights from measurements of the lower central and lateral incisors and canines. The method was used in the case "Josef Mengele", to complement estimates. Tested in the Brazilian population, 70% of match between the actual and the estimated stature were obtained. Using more precise instruments, in the modified method, 96% of correct matching were verified. Recently, a new formula was introduced to estimate height, from measurements of upper teeth, because the technique cannot be used when jaw is not available. The correlation between height and dental dimensions is demonstrated. However, there is still a lack in scientific literature in this field, and further studies are necessary. The estimate of height from dental dimensions can be very useful and important, especially in situations where the complete skeleton it not found, and long bones are not available.

Osteologia do neurocrânio de Iguana iguana iguana (Squamata: Iguanidae)

Skull represents the segment with conspicuous adaptations that, in lizards, may be conservative or promoted by selective pressures. The aim of assisting the morphological knowledge of reptiles, we provide a detailed description of the neurocranium of Iguana iguana iguana based on analysis of three dried adult skeletons. The skull of this species has basal characteristics in lizards without closure of cranial openings and general triangular shape. Bony structures that form the caudal base have many fusions, especially on the floor. In the caudal face the exoccipital and the opisthotic are fused and form the otooccipital, which contributes to the formation of the lateral part of the condyle. The central part is formed by the condyle supraocciopital. Fusions and skeletal structures in Iguana are similar to other lizards. There are no autopomorphies in the neurocranium for this species.

Ditregra - An auxiliary program for structural determination of diterpenes

This work describes the creation of heuristics rules based on 13C-NMR spectroscopy that characterize several skeletal types of diterpenes. Using a collection of 2745 spectra we built a database linked to the expert system SISTEMAT. Several programs were applied to the database in order to discover characteristic signals that identify with a good performance, a large diversity of skeletal types. The heuristic approach used was able to differentiate groups of skeletons based firstly on the number of primary, secondary, tertiary and quaternary carbons, and secondly the program searches, for each group, if there are ranges of chemical shifts that identifies specific skeletal type. The program was checked with 100 new structures recently published and was able to identify the correct skeleton in 65 of the studied cases. When the skeleton has several hundreds of compounds, for example, the labdanes, the program employs the concept of subskeletal, and does not classify in the same group labdanes with double bounds at different positions. The chemical shift ranges for each subskeletal types and the structures of all skeletal types are given. The consultation program can be obtained from the authors. © 1997 - IOS Press. All rights reserved.