Chemical transformations of neolignans

Neolignans, generated by oxydative dimerization of propenylphenol and/or allylphenol, undergo further modifying steps. These biosynthetic reactions, confirmed in vitro, include Cope, retro-Claisen and Claisen rearrangements. Additionally acid catalysis effects convertions of bicyclo [3.2.1] octanoid neolignans into hydrobenzofuranoid neolignans, or inversely of hydrobenzofuranoid neolignans into bicyclo [3.2.1] octanoid neolignans, of hydrobenzofuranoid neolignans into futoenone type neolignans, of tetrahydrofuran neolignans into aryltetralin neolignans, as well as modifications by Friedel - Crafts reactions and the transformation of aryltetralin neolignans into arylindanones by pinacoline - pinacolone type rearrangement.

Synthesis of geranylhydroquinone derivatives with potencial cytotoxic activity

Natural geranylhydroquinone 1 and geranyl-p-methoxyphenol 2 were prepared by Electrophilic Aromatic Substitution (EAS) reactions between geraniol and 1,4-hydroquinone or p-methoxyphenol respectively, using BF3∙Et2O as a catalyst. Furthermore, natural geranylquinone 3, geranyl-1,4-dimethoxyquinone 4 and the new geranyl-4-methoxyphenyl acetate 5 were obtained by chemical transformations of 1 and 2. The compounds were evaluated for their in vitro cytotoxicity activities against cultured human cancer cells of PC-3 human prostate cancer, MCF-7 and MDA-MB-231 breast carcinoma, and Dermal Human Fibroblasts DHF. IC50 values were in the µM range.

An improved strategy for evaluating the extent of chronic arterial baroreceptor denervation in conscious rats

There is no index or criterion of aortic barodenervation, nor can we differentiate among rats that have suffered chronic sham, aortic or sino-aortic denervation. The objective of this study was to develop a procedure to generate at least one quantitative, reproducible and validated index that precisely evaluates the extent of chronic arterial barodenervation performed in conscious rats. Data from 79 conscious male Wistar rats of about 65-70 days of age with diverse extents of chronic arterial barodenervation and used in previous experiments were reanalyzed. The mean arterial pressure (MAP) and the heart rate (HR) of all rats were measured systematically before (over 1 h) and after three consecutive iv bolus injections of phenylephrine (PHE) and sodium nitroprusside (SNP). Four expressions of the effectiveness of barodenervation (MAP lability, PHE ratio, SNP ratio, and SNP-PHE slope) were assessed with linear fixed models, three-level average variance, average separation among levels, outlier box plot analysis, and overlapping graphic analysis. The analysis indicated that a) neither MAP lability nor SNP-PHE slope was affected by the level of chronic sodium intake; b) even though the Box-Cox transformations of both MAP lability [transformed lability index (TLI)] and SNP-PHE slope [transformed general sensitivity index (TGSI), {((3-(ΔHRSNP-ΔHRPHE/ΔMAPSNP-ΔMAPPHE))-0.4-1)/-0.04597}] could be two promising indexes, TGSI proved to be the best index; c) TLI and TGSI were not freely interchangeable indexes for this purpose. TGSI ranges that permit differentiation between sham (10.09 to 11.46), aortic (8.40 to 9.94) and sino-aortic (7.68 to 8.24) barodenervated conscious rats were defined.

Contribuição da fitoquímica para o desenvolvimento de um país emergente

The sustainable development of an emergent country is dependent on a consistent scientific, technologic and innovative policy, on nature and biodiversity, on a rational exploration of natural resources to feeding, social advance and economical aim along with maintenance of health and diseases treatment. Phytochemical investigations may be used to contribute with development throughout undergraduate and graduate career preparing professionals with qualification to these activities, as researcher and professor, including discovering and divulgation of new scientific knowlegments. The role of organic compounds produced by secondary metabolism of plants in the development of new drugs is presented (e. g.) throughout exposition using examples of features involved in this activity, since the recognition of a plant-derived popular medicine, until the laboratory semi-synthesis of its main constituents. Several aspects related to the use of some vegetable species in treatment of many tropical diseases are pointed. Economical and social importance of isolation, structural characterization, pharmacological investigation and chemical transformations of new natural organic substances isolated from the plants are related.

Glicerol: um breve histórico e aplicação em sínteses estereosseletivas

Presently glycerol is considered a co-product of biodiesel industry. As the biodiesel production is exponentially increasing, glycerol generated from the transesterification of vegetable oils and fats is also being produced on a large scale, and turned out to be essential seeking for novel alternatives to the consumption of the extra volume, in crude and/or as derivatives high added value. This review mainly deals with chemical and enzymatic transformations of glycerol to obtain chiral building blocks for synthesis of pharmaceuticals and natural products.

Effect of compaction on microbial activity and carbon and nitrogen transformations in two oxisols with different mineralogy

The use of machinery in agricultural and forest management activities frequently increases soil compaction, resulting in greater soil density and microporosity, which in turn reduces hydraulic conductivity and O2 and CO2 diffusion rates, among other negative effects. Thus, soil compaction has the potential to affect soil microbial activity and the processes involved in organic matter decomposition and nutrient cycling. This study was carried out under controlled conditions to evaluate the effect of soil compaction on microbial activity and carbon (C) and nitrogen (N) mineralization. Two Oxisols with different mineralogy were utilized: a clayey oxidic-gibbsitic Typic Acrustox and a clayey kaolinitic Xantic Haplustox (Latossolo Vermelho-Amarelo ácrico - LVA, and Latossolo Amarelo distrófico - LA, respectively, in the Brazil Soil Classification System). Eight treatments (compaction levels) were assessed for each soil type in a complete block design, with six repetitions. The experimental unit consisted of PVC rings (height 6 cm, internal diameter 4.55 cm, volume 97.6 cm³). The PVC rings were filled with enough soil mass to reach a final density of 1.05 and 1.10 kg dm-3, respectively, in the LVA and LA. Then the soil samples were wetted (0.20 kg kg-1 = 80 % of field capacity) and compacted by a hydraulic press at pressures of 0, 60, 120, 240, 360, 540, 720 and 900 kPa. After soil compression the new bulk density was calculated according to the new volume occupied by the soil. Subsequently each PVC ring was placed within a 1 L plastic pot which was then tightly closed. The soils were incubated under aerobic conditions for 35 days and the basal respiration rate (CO2-C production) was estimated in the last two weeks. After the incubation period, the following soil chemical and microbiological properties were detremined: soil microbial biomass C (C MIC), total soil organic C (TOC), total N, and mineral N (NH4+-N and NO3--N). After that, mineral N, organic N and the rate of net N mineralization was calculated. Soil compaction increased NH4+-N and net N mineralization in both, LVA and LA, and NO3--N in the LVA; diminished the rate of TOC loss in both soils and the concentration of NO3--N in the LA and CO2-C in the LVA. It also decreased the C MIC at higher compaction levels in the LA. Thus, soil compaction decreases the TOC turnover probably due to increased physical protection of soil organic matter and lower aerobic microbial activity. Therefore, it is possible to conclude that under controlled conditions, the oxidic-gibbsitic Oxisol (LVA) was more susceptible to the effects of high compaction than the kaolinitic (LA) as far as organic matter cycling is concerned; and compaction pressures above 540 kPa reduced the total and organic nitrogen in the kaolinitic soil (LA), which was attributed to gaseous N losses.

Influence of the Al content on the phase transformations in Cu-Al-Ag alloys

The influence of the Al content on the phase transformations in Cu-Al-Ag alloys was studied by classical differential thermal analysis (DTA), optical microscopy (OM) and X-ray diffractometry (XRD). The results indicated that the increase in the Al content and the presence of Ag decrease the rate of the b1 phase decomposition reaction and contribute for the raise of this transition temperature, thus decreasing the stability range of the perlitic phase resulted from the b1 decomposition reaction.

Character transformations and their functional significance as a key to the evolution of hystricognath Rodentia

Hystricognathi represent a monophyletic taxon within Rodentia. Since phylogenetically analyzed morphological systems are essential for revealing evolutionary processes, this study identifies evolutionary character transformations on the stem lineage of Hystricognathi as derived from the author's own work and the literature. Data so far indicate that evolutionary transformations in the rostral head region, the loss of tactile ability in the outer nasal skin and the mobile arrangement of the associated cartilage, were allied with a switch from omnivorous to herbivorous and fiber-rich nutrition. Additional character transformations in the skull assist in digesting such food. Structures associated with reproduction and placentation show a remarkable pro portion of derived character conditions: the chorioallantoic placenta has a ring-shaped organization and growth structure which optimizes the capacity for passive diffusion, a subplacenta occurred as a specialized region responsible for placental invasion and the inverted yolk sac facilitates substance exchange with the main placenta. Finally, precocial newborns evolved as a derived condition within Rodentia. All things considered, a mode of reproduction is indicated, which does not demand excessive additional energy intake by the mother and is in accordance with her low energetic diet. Hystricognathi possess major character transformations that represent prerequisites for their successful radiation at the time when more open ecosystems and grasslands evolved during Earth history. The analysis resulted in the reconstruction of a life-near picture of the hystricognath stem species pattern with high explanatory power in terms of changes in space and time and their interdependence with biodiversity.

Economic crisis and counter-reform of universal health care systems: Spanish case

The economic crisis that has been affecting Europe in the 21st century has modified social protection systems in the countries that adopted, in the 20th century, universal health care system models, such as Spain. This communication presents some recent transformations, which were caused by changes in Spanish law. Those changes relate to the access to health care services, mainly in regards to the provision of care to foreigners, to financial contribution from users for health care services, and to pharmaceutical assistance. In crisis situations, reforms are observed to follow a trend which restricts rights and deepens social inequalities.

Changes in the relationship between society and nature in the Mezzo-region of Southeastern Pará, Amazon, Brazil

With this work, the authors wish to show some of the alterations in the pattern of relations between society and nature, which have taken place throughout the 20th century in the Parauapebas and Itacaiúnas river valleys, as well as in parts of the Tocantins River valley, in southeastern Pará. This is accomplished through descriptions based on Coudreau's first-hand accounts (1889), transcribed in "Voyage a Itaboca et a L'Itacayuna", published in 1897, which depicts an area almost totally covered by forest. This is followed by a counter view made possible through the LandSat 5 satellite sensors, with images of those valleys in 2001, showing the consequences of society transformations and pressure on natural resources, and above all the dramatic decrease in the size of the forest, reduced to 52 percent of the 63,000 square kilometers analyzed herein.

Canine experimental infection: intradermal inoculation of Leishmania infantum promastigotes

Five mixed breed dogs were inoculated intradermally (ID) with cultured virulent stationary phase promastigotes of Leishmania infantum Nicole, 1908 stocks recently isolated. Parasite transformations in the skin of ID infected dogs were monitored from the moment of inoculation and for 48 h, by skin biopsies. Anti-Leishmania antibody levels were measured by indirect immunofluorescence assay, counterimmunoelectrophoresis and direct agglutination test, and clinical conditions were examined. Thirty minutes after ID inoculation the first amastigotes were visualised and 3 to 4 h after inoculation the promastigotes were phagocyted by neutrophils and by a few macrophages. These cells parasitised by amastigotes progressively disappeared from the skin and 24 h after inoculation parasites were no longer observed. Local granulomes were not observed, however, serological conversion for antibodies anti-Leishmania was achieved in all dogs. Direct agglutination test was the only technique positive in all inoculated dogs. Amastigotes were found in the popliteal lymph node in one dog three months after inoculation. This work demonstrates that, with this inoculum, the promastigotes were transformed into amastigotes and were up taken by neutrophils and macrophages. The surviving parasites may have been disseminated in the canine organism, eliciting a humoral response in all cases.

Transformations in occluded light fraction organic matter in a clayey oxisol: evidence from 13C-CPMAS-NMR and delta13C Signature

We hypothesised that, during occlusion inside granular aggregates of oxide-rich soils, the light fraction organic matter would undergo a strong process of decomposition, either due to the slow process of aggregate formation and stabilisation or due to digestion in the macro- and meso-fauna guts. This process would favour the accumulation of recalcitrant materials inside aggregates. The aim of this study was to compare the dynamics and the chemical composition of free and occluded light fraction organic matter in a natural cerrado vegetation (woodland savannah) and a nearby pasture (Brachiaria spp.) to elucidate the transformations during occlusion of light fraction in aggregates of a clayey Oxisol. Nuclear Magnetic Resonance of the 13C, with Cross Polarisation and Magic Angle Spinning (13C-CPMAS-NMR), and 13C/12C isotopic ratio were combined to study organic matter composition and changes in carbon dynamics, respectively. The occluded light fraction had a slower turnover than the free light fraction and the heavy fraction. Organic matter in the occluded fraction also showed a higher degree of decomposition. The results confirm that processes of soil organic matter occlusion in the typical "very fine strong granular" structure of the studied oxide-rich soil led to an intense transformation, selectively preserving stable organic matter. The small amount of organic material stored as occluded light faction, as well as its stability, suggests that this is not an important or manageable sink for sequestration of atmospheric CO2.

Soil structure transformations from ferralic to nitic horizons on a toposequence in southeastern Brazil

The soil structure transformation from ferralic to nitic horizons was studied in a toposequence on quaternary red clayey sediments and diabase in Piracicaba (SP), Brazil. Morphological and micromorphological studies, image analysis, soil water characteristic curves and monitoring of (total) soil water potential head were used. The presence of polyconcave vughs, clayskins and planar voids shows that the vertical and lateral transition and structural transformation from ferralic to nitic horizons is given by the coalescence of the microaggregates, probably due to tensions created in a drier period in the past. Changes to a more humid climate with a defined dry season and alternate drying and wetting cycles resulted in the fissuration of the previously coalesced material, forming polyhedral aggregates and microaggregates. Simultaneously, clay illuviation filled the voids and together with the compacting action of the biological activity of these soils contributed to the coalescence of microaggregates.

Pyrrolizidine alkaloids of senecio sp from Peru

Six pyrrolizidine alkaloids (PAs) (two saturated macrocyclic, three unsaturated macrocyclic and one unsaturated seco-macrocyclic) were isolated from native Peruvian Senecio species. The structures of these alkaloids were established by a complete NMR spectroscopic analysis, chemical transformations and comparison of their NMR data with those published for similar alkaloids. Three PAs were then tested for antifungal activity against Fusarium moniliforme, F. (Sheldon), F. oxysporum fs. lycopersici (Scheldt) and F. solani (Mart), no significant activity being observed.