Reduction of mercury(II) by tropical river humic substances (Rio Negro) - Part II. Influence of structural features (molecular size, aromaticity, phenolic groups, organically bound sulfur)

The influence of structural features of tropical river humic substances (HS) on their capability to reduce mercury(II) in aqueous solutions was studied. The HS investigated were conventionally isolated from Rio Negro water-Amazonas State/Brazil by means of the collector XAD 8. In addition, the isolated HS were on-line fractionated by tangential-flow multistage ultrafiltration (nominal molecular-weight cut-offs: 100, 50, 30, 10, 5 kDa) and characterized by potentiometry and UV/VIS spectroscopy. The reduction of Hg(II) ions to elemental Hg by size-fractions of Rio Negro HS was assessed by cold-vapor AAS (CVAAS). UV/VIS spectrometry revealed that the fractions of high molecular-size (F-1 > 100 kDa and F-2: 50-100 kDa) have a higher aromaticity compared to the fractions of small molecular-size (F-5: 5-10 kDa, F-6: < 5 kDa). In contrast, the potentiometric study showed different concentration of functional groups in the studied HS fractions. The reduction of Hg(II) by aquatic HS fractions at pH 5 proceeded in two steps (I, II) of slow first order kinetics (t(1/2) of I: 160 min, t(1/2) of II: 300 min) weakly influenced by the molecular-size, in contrast to the differing degree of Hg(II) reduction (F-5 > F-2 > > F-1 > F-3 > F-4 > > F-6). Accordingly, Hg(II) ions were preferably reduced by HS molecules having a relatively high ratio of phenolic/carboxylic groups and a small concentration of sulfur. From these results a complex 'competition' between reduction and complexation of mercury(II) by aquatic HS occurring in tropical rivers such as the Rio Negro can be suggested. (C) 2003 Elsevier B.V. All rights reserved.

Antifungal amide from leaves of Piper hispidum

Bioactivity-guided fractionation of a CH2Cl2 extract from leaves of Piper hispidum (Piperaceae) yielded a new pyrrolidine amide, N-[7-(3',4'-methylenedioxyphenyl)-2(Z),4(Z)-heptadienoyl] pyrrolidine 1, in addition to two known amides N-[5-(3',4'-methylenedioxyphenyl)-2(E)-pentadienoyl]pyrrolidine and N-[2-(3',4'-methylenedioxy-6'-methoxyphenyl)-2(Z)-propenoyl]pyrrolidine. The structure of compound 1 was elucidated by interpretation of spectral data, including ES-MS. Compound 1 showed antifungal activity against Cladosporium sphaerospermum.

Antifungal amides from Piper arboreum and Piper tuberculatum

In continuation of our study of the Piperaceae we have isolated several amides, mainly those bearing isobutyl, pyrrolidine, dihydropyridone and piperidine moieties. Bioactivity-guided fractionation of extracts from leaves of Piper arboreum yielded two new amides, N-[10-(13,14-methylenedioxyphenyl)-7(E),9(Z)-pentadienoyl]-pyrrolidine (1), arboreumine (2) together with the known compounds N-[10-(13,14-methylenedioxyphenyl)-7(E)-pentaenoyl]-pyrrolidine (3) and N-[10-(13,14-methylenedioxyphenyl)-7(L, 9(E)-pentadienoyl]-pyrrolidine (4). Catalytic hydrogenation of 3 yielded the amide iV-[10-(13,14-methylenedioxyphenyl)-pentanoyl]-pyrrolidine (5). We also have isolated six amides (6-11) and two antifungal cinnamoyl derivatives (12, 13) from seeds and leaves of Piper tuberculatum. Compounds 1-11 showed antifungal activity as determined by direct bioautography against Cladosporium sphaerospermum while compounds 3-4 and 6-13 also showed antifungal activity against C. cladosporioides. (C) 2002 Published by Elsevier B.V. Ltd.

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Tillage and phosphorus management effects on enzyme-labile bioactive phosphorus availability in Cerrado Oxisols

Phosphorus (P) is an essential element in crop nutrition, which can be growth limiting or an environmental contaminant, if present in excess. Tillage practices have a direct effect on the behavior and availability of soil P. Sorption and availability of various P forms were evaluated in an incubation-fractionation study of three soils, a Typic Paleudults (CR soil) and two Cerrado Oxisols (Latossolo Vermelho-Amarelo [LVA] and Latossolo Vermelho [LV]) with distinct biogeochemical characteristics and tillage management history. Phosphate and myo-inositol hexakisphosphate (mIPH) were strongly sorbed by the soils. Maximum adsorption capacities (S(max)) were 2.2-6.9, 3.3-7.8, and 1.6-19.8 mmol kg(-1) for phosphate in the 0-40 cm depths of the CR, LV, and LVA soils, respectively. For mIPH, S. were 1.2-3.7, 3.7-5.5, and 4.6-5.2 mmol kg(-1). Saturation indices reflected the long-term effect of repeated manure applications on the Paleudults and the near saturation of its P holding capacity, in contrast to the recently cultivated Cerrado soils. Tillage method appeared to have altered P retention characteristics of the near-surface zone very slightly, while increases in ligand-exchangeable (EEP;) and enzyme-labile organic P (EDTA-PHP) forms were observed in no-till Oxisols. In the Paleudults, added manure P increased bioactive P fractions and P saturation of no-till near-surface soil zone. Estimates of all bioactive P fractions using the ligand-based enzymatic assay showed it to be an effective method for assessing P availability in soil and developing sustainable P management strategies, particularly in Cerrado Oxisols that were low in organic matter while having an extensive P-fixing capacity. Published by Elsevier B.V.

Speciation of lead in seawater and river water by using Saccharomyces cerevisiae immobilized in agarose gel as a binding agent in the diffusive gradients in thin films technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Giant first-forbidden resonances

Recent experimental data on first-forbidden charge-exchange resonances are discussed in the framework of a schematic model. We also evaluate the screening of the weak coupling constants induced by both the giant resonances and the Δ-isobar. It is shown that the last effect does not depend on the multipolarity of the one-particle moment. Due to the same reason, the fraction of the reaction strength pushed up into the Δ-resonance region is always the same regardless of the quantum numbers carried by the excitation. Simple expressions are derived for the dependence of the excitation energies of the first-forbidden giant resonances on the mass number and isospin of the target. The model reproduces consistently both the Gamow-Teller and the first-forbidden resonances. © 1983.

Os complexos granitoides Cunhaporanga e Tres Corregos (PR) zoneamento magmatico e implicacoes geotectonicas

Geological, petrographic, chemical and zircon typology data from the Cunhaporanga and Tres Corregos granitoid complexes are presented and discussed. Both complexes of Late Precambrian age evolved by crystal fractionation. By its zircon typology the Cunhaporanga is classified as a low temperature calc-alkaline batholith and the Tres Corregos as a medium temperature calc-alkaline complex. This classification implies a major participation of mantle material during the generation of the Tres Corregos magma in relation to the Cunhaporanga ones. In this way both complexes define a magmatic zoning from NW to SE done by a increasing in the depth of magma generation. -from English summary

Bioactive guanidine alkaloids from Pterogyne nitens

Bioactivity-guided fractionation of a methanolic CHCl 3 extract of the leaves of Pterogyne nitens afforded the known guanidine alkaloid pterogynidine [2] and three new guanidine alkaloids, nitensidines A [3], B [4], and C [5], all of which exhibited selective activity towards the DNA repair-deficient yeast mutant RS 321 (IC 12=9.3-20.0 μg/ml); 3,4, and 5 were moderately cytotoxic to CHO Aux B 1 cells (IC 50=8.5-13.0 μg/ml).

A simple solution for the flavor question

We consider a simple way of solving the flavor question by embedding the three-family standard model in a semisimple gauge group extending minimally the weak isospin factor. Quantum chiral anomalies between families of fermions cancel with a matching of the number of families and the number of color degrees of freedom. Our demonstration shows how the theory leads to determination of families structure when the standard model is the input at low energies. The new physics is limited to start below a few TeVs within the reach of the next generation colliders.

Neolignans from leaves of Ocotea catharinensis

A hexane extract of Ocotea catharinensis leaves afforded, by chromatographic fractionation, 11 neolignans, eight of the benzofuran- type (including three new compounds) and three of the bicyclo[3.2.1] octane-type (including two new compounds).

Geochemical Variability of the Rapakivi Itu Province, State of São Paulo, SE Brazil

This paper describes the chemical variability of the Late Precambrian Itu Rapakivi Province (IRP), State of São Paulo, SE Brazil, based on 187 selected analyses from the Itu, São Francisco, Sorocaba, Campina do Veado and Sguario/ Correa granites. The IRP has an almost uniform petrographic character conferred by the overall dominance of subalkaline biotite granites. Monzogranites (adamellites), granodiorites, quartz syenites, quartz monzonites are rare to very rare rock types and tonalites and quartz diorites are almost restricted to enclaves. Typical chemical features are the high FeO*/MgO ratio, a clustering of the K2O values between 4.5 and 6.0 wt.% and K2O/Na2O ratios which define the IRP as mildly potassic although more potassic rocks also occur. The overal Peacock Alkalinity Index is 54 defining the Province as alkali-calcic. In the Shand diagram the data cluster near the metaluminous/peraluminous boundary. Relationships between Nb, Rb and Y stress the within plate character of the IRP and the relationships between Rb, Ba and Sr reveal the importance of feldspar fractionation in magma evolution. The data also show an interbody and an intrabody chemical variability due to the variation in the composition of the crustal magma protoliths, as assigned by K/Rb relations. The presence of several magmatic cycles which built up the major intrusions reflects a magma ascent from collecting chambers successively drained and recharged, a feature in agreement with the clear link between the bodies and long lived, successively reactivated, transcurrent faults. Most of the chemical features of the IRP correspond to those of the classical Finnish rapakivi granites.

Lead- and copper-complexing extracellular ligands released by Kirchneriella aperta (Chloroccocales, Chlorophyta)

The freshwater planktonic alga Kirchneriella aperta was grown in batch cultures to stationary growth phase. Copper and lead complexation properties of the exudate from stationary and exponential growth phases were determined by titrations monitored by ion-selective electrodes. Molecular weight fractionation dialysis) and analysis of the titration data (Scatchard Plot) revealed that K. aperta releases metal-complexing ligands. Copper is associated with low and high molecular weight compounds, whereas lead forms complexes with only high molecular weight compounds. Gas-liquid chromatography showed that mannose and rhamnose make up 74% of the total high molecular weight organic material, with uronic acids present at 19%.

Search for Antifungal and Anticancer Compounds from Native Plant Species of Cerrado and Atlantic Forest

Bioactivity-guided fractionation of several bioactive extracts obtained from Cerrado and Atlantic Forest plant species led to the isolation of potent DNA-damaging piperidine 1-5 and guanidine alkaloids 6-9 from Cassia leptophylla and Pterogyne nitens respectively, two common Leguminosae from Atlantic Forest. By means of biotechnological approach on Maytenus aquifolium, a species from Cerrado, moderate DNA-damaging sesquiterpene pyridine alkaloid 10-11 was isolated. Bioassay-guided fractionation on Casearia sylvestris, a medicinal plant species found in Cerrado and Atlantic Forest, led to the isolation of clerodane diterpenes 12-13 which showed effect on DNA. In addition, we have reported several interesting potent antifungal iridoids: 1β-hydroxy-dihydrocornin (14), 1α-hydroxy-dihydrocornin (15), α-gardiol (16), β-gardiol (17), plumericin (18), isoplumericin (19), 11-O-trans-caffeoylteucrein (20); ester derivative: 2-methyl-4-hydroxy-butyl-caffeoate (21), amide N-[7-(3'.4'-methylenedioxyphenyl)-2Z, 4Z-heptadienoyl] pyrrolidine (22) and triterpene viburgenin (23).

Cromatografia em contra-corrente de gotejamento na separação de substâncias fenólicas de Neuropogon aurantiaco-ater

This work reports the separation of phenolic compounds present in the metabolic extract of the lichen Neuropogon aurantiaco-ater (Usniaceae). The crude extract was fractionated by droplet counter-current chromatography using a solvent mixture of high polarity (chloroform:methanol:water at 43:37:20, in ascending mode). The separation resulted in the isolation of usnic and protocetratic acid, which were identified by TLC, HPLC, and NMR tests.