Substâncias húmicas aquáticas: fracionamento molecular e caracterização de rearranjos internos após complexação com íons metálicos

The aquatic humic substances (AHS) investigated in this study were conventionally isolated from Rio Negro waters - Amazonas State/Brazil by means of the collector XAD 8. A special five-stage tangential-flow ultrafiltration device was used for analytical fractionation of AHS. The fractionation patterns (6 fractions each) showed that metal traces remaining in AHS after their XAD 8 isolation have different size distributions. For instance, the major percentage of traces of Ni, Cu, Zn, Cd and Pb (determined using ICP-AES) was preferably complexed by molecules with relatively high molecular size (30-100 kDa) and the following complexation order was characterized: F2 >> F1 = F4 = F5 > F3 > F6. Moreover, the species formed between AHS and metals prepared by spiking, showed distribution patterns changing as a function of the complexation time (ageing process), indicating a slow transformation process and an inner rearrangements in the binding sites within the AHS molecules.

Derivado cinamoílico com atividade no reparo de DNA e outras substâncias de Cinnamomum australe (Lauraceae)

The bioactive compound trans-3'-methylsulphonylallyl trans-cinnamate (1) along with the inactives iryelliptin (2) and (7R,8S,1'S)-delta8'-3',5'-dimethoxy-1',4'-dihydro-4'-oxo-7.0.2',8.1'-neolignan (3) were isolated from the leaves of Cinnamomum australe. The structures of these compounds were assigned by analysis of 1D and 2D NMR data and comparison with data registered in the literature for these compounds. The DNA-damaging activity of 1 is being described for the first time.

Esquema para interpretação de espectros de substâncias orgânicas na região do infravermelho

This article decribes a simple and systematic method to interpret an infrared spectrum using a flow chart to elucidate the structure of a simple organic compound. It is aimed at undergraduate courses of organic chemistry to make beginners proficient. The proposed flow chart for infrared spectrum interpretation and characterization of organic compounds is suitable for theoretical and experimental courses.

Espectrometria de massas com ionização por "electrospray": processos químicos envolvidos na formação de íons de substâncias orgânicas de baixo peso molecular

An overview of the current literature on the chemical processes involved in the ion formation from low molecular weight organic compounds by electrospray ionization mass spectrometry is given.

Cromatografia em leito móvel simulado na produção de substâncias enantiomericamente puras ou enriquecidas em larga escala

There is great interest nowadays in the use of preparative liquid chromatography as an effective tool for the production of enantiomerically pure, or enriched, compounds for the pharmaceutical industry. To make the chromatographic process economically attractive, attention is now focused on the choice of the chromatographic operating mode to minimize eluent consumption and to maximize productivity. Among the alternatives to the traditional batch chromatography, attention is now shifting towards simulated moving bed (SMB) technologies and a review covering the latest developments in this area seems timely. Several aspects of this important analytical technique are presented and details concerning the SMB technology for process optimization are outlined.

Estudo da labilidade de Cu(II), Cd(II), Mn(II) e Ni(II) em substâncias húmicas aquáticas utilizando-se membranas celulósicas organomodificadas

In this work commercial filters papers were organomodified with tetraethylorthosilicate (TEOS) and 3-aminopropyltriethoxysilane (3-APTS), aiming at the development of a new analytical procedure for in-situ speciation of labile and inert metal species in aquatic systems. Parameters that exert influence on the metal lability such as pH, chelating time, concentration and characteristics of the organic matter were studied in the laboratory using tests for metal recuperation. The results showed slower kinetics for Cu ion than for Ni, Mn and Cd in the absence of aquatic humic substances (AHS). The relative lability observed for complexed metals in aquatic humic substances using organomodified filter papers was Cu>>Cd>Ni>Mn. The pH values, structural characteristics and concentration of AHS exert strong influence on the lability of the metals. The results obtained showed that the utilization of organomodified filter papers can be an interesting and promising alternative for in situ characterization of metal lability in aquatic systems.

Atropoisomerismo: o efeito da quiralidade axial em substâncias bioativas

Atropisomerism is a special kind of stereoisomeric relationship that arises from the freezing of a certain conformation of an organic molecule, associated with a high rotational barrier about a single covalent bond. Atropisomerism has been originally described in orto-functionalyzed biphenyl derivatives, but a lot of other organic functionalities can present this structural phenomenon, characterized by the presence of chiral properties in compounds that don't present classical stereogenic centers. Atropisomeric compounds, intermediates and catalysts have well-know importance in organic synthesis, but the influence of the axial chirality in substances able to modulate biological systems is still not very exploited in drug design and development. In this context, the present account describes the importance of this structural property in the medicinal chemistry of different classes of bioactive compounds or therapeutic agents, emphasizing how atropisomerism could affect the molecular recognition of a ligand or a prototype by the target bioreceptor.

Identificação de substâncias em análise toxicológica sistemática utilizando um sistema informatizado para cálculo de parâmetros cromatográficos e busca em bases de dados

In spite of the availability of large databases of chromatographic data on several standardized systems, one major task in systematic toxicological analysis remains, namely how to handle the experimental data and retrieve data from the large available databases in a meaningful and productive way. To achieve this purpose, our group proposed an Internet-based tool using previously published STA databases, which interlaboratorial reproducibility tests have already evaluated. The developed software has the capability to calculate corrected chromatographic parameters, after the input of data obtained with standard mixtures of calibrators, and search the databases, currently incorporating TLC, color reactions, GC and HPLC data. At the end of the process, a list with candidate substances and their similarity indexes is presented.

Esquema geral para elucidação de substâncias orgânicas usando métodos espectroscópico e espectrométrico

This work describes a systematic method to be applied in undergraduate courses of organic chemistry, correlating infrared spectra, hydrogen and carbon-13 nuclear magnetic resonance, and mass spectra. To this end, a scheme and a table were developed to conduct the elucidation of the structure of organic compounds initially using infrared spectra. Interpretation of hydrogen and carbon-13 nuclear magnetic resonance spectra and of mass spectra is used to confirm the proposed structure.

Elucidação estrutural de substâncias orgânicas com auxílio de computador: evoluções recentes

The development of new tools for chemoinformatics, allied to the use of different algorithms and computer programmes for structure elucidation of organic compounds, is growing fast worldwide. Massive efforts in research and development are currently being pursued both by academia and the so-called chemistry software development companies. The demystification of this environment provoked by the availability of software packages and a vast array of publications exert a positive impact on chemistry. In this work, an overview concerning the more classical approaches as well as new strategies on computer-based tools for structure elucidation of organic compounds is presented. Historical background is also taken into account since these techniques began to develop around four decades ago. Attention will be paid to companies which develop, distribute or commercialize software as well as web-based and open access tools which are currently available to chemists.

Substâncias tóxicas persistentes (STP) no Brasil

The present article presents an assessment of PTS in Brazil including polychlorinated biphenyls, polycyclic aromatic hydrocarbons, benzene hexachloride, aldrin, dieldrin, endrin, p,p,-DDT, p,p,DDE, p,p,-DDD, hexachlorocyclohexanes (alpha-HCH, beta-HCH, gamma-HCH and delta-HCH), endossulfan, heptachlor and pentachlorophenol. The data presented here are related to a survey of PTS levels in different environmental matrixes (soil, sediment, water, air, biota) and human tissues (milk, blood, human hair), according to the scope of the UNEP-GEF Regionally Based Assessment of PTSs. Potential sources were evaluated considering national products and imports, since most of the literature does not allow source identification. Finally, Brazilian legislation was updated.

Piranoflavonas inéditas e atividades tripanocidas das substâncias isoladas de conchocarpus heterophyllus

The phytochemical investigation of trypanocidal extracts from leaves and stems of Conchocarpus heterophyllus (A. St.-Hil.) Kallunki & Pirani (Rutaceae) afforded new pyranoflavones along with the known compounds flavone, 7-methoxyflavone, 5-hydroxyflavone, haplotusine, 1-methyl-2-phenyl-4-quinolone alkaloid, beta-sitosterol, stigmasterol, and beta-sitosteryl benzoate. Their structures were established based on their spectral data. NMR data for the alkaloid haplotusine and the new pyranoflavones are described for the first time herein. These compounds were assayed on the tripomastigote forms of Trypanosoma cruzi. Among them, haplotusine and 1-methyl-2-phenyl-4-quinolone showed moderate values of IC50 136.9 and 144.9 mM, respectively.

Saponinas antifúngicas de Swartzia langsdorffii

Chromatographic fractionation of the EtOH extract from the leaves of Swartzia langsdorffii afforded the pentacyclic triterpenes oleanolic acid and lupeol, and two saponins: oleanolic acid 3-sophoroside and the new ester 3-O-b-D-(6'-methyl)-glucopyranosyl-28-O-b-D-glucopyranosyl-oleanate. Their structures were elucidated from spectral data, including 2D NMR and HRESIMS experiments. Antifungal activity of all isolated compounds was evaluated, using phytopathogens Cladosporium cladosporioides and C. sphaerospermum, and human pathogens Candida albicans, C. krusei, C. parapsilosis and Cryptococcus neoformans.

Estudo comparativo de técnicas de screening para avaliação da atividade anti-bacteriana de extratos brutos de espécies vegetais e de substâncias puras

In this work, the effectiveness of four screening techniques (three techniques of the diffusion method and one microdilution broth method) were compared. Evaluated were the ethanolic and dichloromethanic extracts of Miconia rubiginosa (Melastomataceae) against six standard bacteria (ATCC). The results showed statistical disagreement among the three diffusion techniques. Among the diffusion techniques, the well technique displayed the best result. However the microdilution broth method demonstrated to be the most adequate method to evaluate the antibacterial activity of plant crude extracts and pure compounds when compared to the other methodologies.

Análise de fluorescência de substâncias húmicas extraídas da água, solo e sedimento da Lagoa dos Patos - MS

The humic substances were extracted from sediments, water and soil close to the Lagoa dos Patos-MS. The characterization was performed through fluorescence emission. In the HSs it is possible to see strong indications of incorporation of compounds originating from lignin degradation, confirmed by fluorescence emission (EEM and synchronous spectra). These differences observed in HSs may be due to tropical regions displaying a great variety of vascular plants and aquatic macrophytes that contribute natural organic matter. The seasonality effect also causes the entrance of pedogenic material and the suspension of sediments by the action of winds.