Chemical and in vitro study of the potential of 3-(aryl)-2-sulfanylpropenoic acids and their Zn(II) complexes as protective agents against cadmium toxicity

The free H(2)xspa ligands [xspa = pspa, Clpspa, tspa or fspa where p = 3-(phenyl), Clp = 3-(2-chlorophenyl), t = 3-(2-thienyl), f = 3-(2-furyl) and spa = 2-sulfanylpropenoato], their Zn(II) complexes of formula [HQ](2)[Zn(xspa)(2)] (HQ=diisopropylammonium) and the Cd(II) equivalents were prepared and characterized by elemental analysis and by IR, Raman and NMR ((1)H, (13)C) spectroscopy. X-Ray studies of the crystal structures of [HQ](2)[Zn(pspa)(2)], [HQ](2)[Zn(Clpspa)2], [HQ](2)[Zn(tspa)(2)] and [HQ](2)[Zn(fspa)(2)] show that the zinc atom is coordinated to two O atoms and two S atoms of the ligands in a distorted tetrahedral ZnO(2)S(2) environment. In the structures of [HQ](2)[Cd(pspa)(2)] and [HQ](2)[Cd(Clpspa)(2)] the cadmium atom is coordinated to three S atoms and two carboxylato O atoms of the ligands in a distorted trigonal bipyramidal environment. The interchange of ligands between Zn( II) and Cd( II) was studied by (113)Cd NMR spectroscopy. The in vitro protective effect of H(2)xspa and their Zn( II) complexes against Cd toxicity was investigated using the human hepatocarcinoma HepG2 cell line and the pig renal proximal tubule LLC-PK1 cell line. The incorporation of Zn( II) was found to be relevant in the case of H(2)pspa, with an increase observed in the cell viability of the LCC-PK1 cells with respect to the value for the free ligand.

Chemical analyses confirm a rare case of seed dispersal by bees

It has been suggested that dispersal of seeds of Coussapoa asperifolia magnifolia could have endozoochoric dispersal by frugivorous birds and monkeys because the fruits are red when ripe, or exozoochoric dispersal, because the exocarp is mucilaginous and sticky. However, our field observations showed only stingless bees collecting the exocarp with seeds of C. asperifolia magnifolia, which are used for building and repairing their nests, from which the plants sprout. This paper aimed to determine the fruit chemical composition, since we postulated that C. asperifolia magnifolia is neither consumed by birds nor monkeys due to being very sticky and apparently resinous. Apolar extract analyses revealed the fruits are not resinous but extremely rich in waxes ( mainly esterified triglycerides), and polar extract analyses revealed the sugar content to be close to the sensorial minimum level. This probably accounts for why only stingless bees are seen visiting fruits and dispersing seeds.

CHEMICAL AND PHYSICO-CHEMICAL CHARACTERIZATION OF LIGNINS OBTAINED FROM ETHANOL-WATER FRACTIONATION OF BAGASSE

Organosolv lignins can replace petroleum chemicals such as phenol either partially or totally in various applications. Eight lignins, seven of which corresponded to the ethanol-water fractionation of bagasse and the other to a reference lignin (Alcell (R)) were analyzed with the aim to evaluate their chemical and physicochemical characteristics. The purity of the lignin fractions was determined by high pressure liquid chromatography (HPLC) and by ash content. Fourier Transform-Infrared Spectroscopy (FTIR) techniques and differential UV spectroscopy were applied to identify the chemical groups in the lignin samples. The molecular weight distribution was determined by size exclusion chromatography (HPSEC). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to determine the mass loss due to the high temperature treatment. The lignins studied showed the presence of p-hydroxyphenyl (H unit) and a greater proportion of guaiacyl (G unit) moieties, lower purity, similar or greater amount of phenolic hydroxyl groups, and higher degradation temperatures, than the Alcell (R) lignin.

Total soil carbon and chemical attributes under different land uses in the Brazilian savanna

Total soil carbon and chemical attributes under different land uses in the Brazilian savanna. The Brazilian savanna region (Cerrado) is one of the largest cultivated areas of the world. The different land uses in the region can effectively change the quantities of soil organic matter and the cycling of nutrients. I-lie objective of this study was to evaluate the effect of different land use management systems on the relationship between soil organic carbon and the soil chemical attributes of a Red Latosol (Oxisol) under Cerrado in Rio Verde (Goias state). The treatments studied were native vegetation (cerrado), low-productivity pasture, conventional tillage with soybean, and no-tillage with soybean and maize. The smallest values for pH, available P, K, Ca and Mg were observed for the Cerradao treatment, even if the relatively high C levels increased the potential soil cation exchange capacity. The pasture, conventional tillage and no-tillage treatments showed higher K, Ca, Mg, available 13, and S concentrations in the soil. In the areas where soil tillage did not take place and lime and fertilizers were applied superficially, the stratification of the soil organic carbon provides the retention of the elements near to the surface, with significance correlations with the soil chemicals attributes.

Effects of land cover on chemical characteristics of streams in the Cerrado region of Brazil

The Cerrado is the second largest Brazilian biome and contains the headwaters of three major hydrological basins in Brazil. In spite of the biological and ecological relevance of this biome, there is little information about how land use changes affect the chemistry of low-order streams in the Cerrado. To evaluate these effects streams that drain areas under natural, rural, and urban land cover were sampled near Brasilia, Brazil. Water samples were collected between September 2004 and December 2006. Chemical concentrations generally followed the pattern of Urban > Rural > Natural. Median conductivity of stream water of 21.6 (interquartile: 22.7) mu S/cm in urban streams was three and five-fold greater relative to rural and natural areas, respectively. In the wet season, despite of increasing discharge, concentration of many solutes were higher, particularly in rural and natural streams. Streams also presented higher total dissolved N (TDN) loads from natural to rural and urban although DIN:DON ratios did not differ significantly. In natural and urban streams TDN was 80 and 77% dissolved organic N, respectively. These results indicate that alterations in land cover from natural to rural and urban are changing stream water chemistry in the Cerrado with increasing solute concentrations, in addition to increased TDN output in areas under urban cover, with potential effects on ecosystem function.

k(0)-INAA for determining chemical elements in bird feathers

The k(0)-method instrumental neutron activation analysis (k(0)-INAA) was employed for determining chemical elements in bird feathers. A collection was obtained taking into account several bird species from wet ecosystems in diverse regions of Brazil. For comparison reason, feathers were actively sampled in a riparian forest from the Marins Stream, Piracicaba, Sao Paulo State, using mist nets specific for capturing birds. Biological certified reference materials were used for assessing the quality of analytical procedure. Quantification of chemical elements was performed using the k(0)-INAA Quantu Software. Sixteen chemical elements, including macro and micronutrients, and trace elements, have been quantified in feathers, in which analytical uncertainties varied from 2% to 40% depending on the chemical element mass fraction. Results indicated high mass fractions of Br (max=7.9 mgkg(-1)), Co (max= 0.47 mg kg(-1)), Cr (max =68 mg kg(-1)), Hg (max =2.79 mg kg(-1)), Sb (max= 0.20 mg kg(-1)), Se (max=1.3 mg kg(-1)) and Zn (max =192 mg kg(-1)) in bird feathers, probably associated with the degree of pollution of the areas evaluated. In order to corroborate the use of k(0)-INAA results in biomonitoring studies using avian community, different factor analysis methods were used to check chemical element source apportionment and locality clustering based on feather chemical composition. (C) 2010 Elsevier B.V. All rights reserved.

Chemical changes in bromeliad leaves at different vegetative stages

Studies concerning the accumulating capacity of native epiphytic bromeliads are of utmost relevance, due to the continuous incorporation of chemical elements provided by these organisms in the ecosystems. Bromeliad species from diverse So Paulo State conservation units, Brazil, were sampled for young, mature and old leaves using a sustainable sampling method. By applying INAA, the accumulation of ten chemical elements, i.e. Br, Ca, Co, Fe, K, Na, Rb, Sc, Sr and Zn, was investigated in different leaf vegetative stages. The bromeliads showed divergent chemical element distribution patterns, demonstrating a real complexity in the accumulation and translocation mechanisms utilized by these plants.

Native bromeliads as biomonitors of airborne chemical elements in a Brazilian restinga forest

Epiphytic bromeliads have been used as biomonitors of air pollution since they have specialized structures in leaves for absorbing humidity and nutrients available in the atmosphere. Leaves of five bromeliad species were collected in the conservation unit Parque Estadual Ilha do Cardoso, Sao Paulo State, Brazil, and analyzed by INAA. Vriesea carinata was the species showing most accumulation, with the highest mass fractions of K, Na, Rb and Zn. Similar results were previously found for the same species collected in the dense ombrophilous forest. Chemical composition of bromeliads provided an indication of the atmosphere status in the conservation unit.

Status of chemical elements in Atlantic Forest tree species near an industrial complex

Environmental quality assessment studies have been conducted with tree species largely distributed in the Atlantic Forest. Leaf and soil samples were collected in the conservation unit Parque Estadual da Serra do Mar (PESM) nearby the industrial complex of Cubatao, Sao Paulo State, Brazil, and analyzed for chemical elements by instrumental neutron activation analysis. Results were compared to background values obtained in the Parque Estadual Carlos Botelho (PECB). The higher As, Fe, Hg and Zn mass fractions in the tree leaves of PESM indicated anthropogenic influence on this conservation unit.

Chemical characterization of agricultural supplies applied to organic tomato cultivation

The agricultural supplies used in the organic system to control pests and diseases as well as to fertilize soil are claimed to be beneficial to plants and innocuous to human health and to the environment. The chemical composition of six agricultural supplies commonly used in the organic tomato culture, was evaluated by instrumental neutron activation analysis (INAA). Results were compared to the maximum limits established by the Environment Control Agency of the Sao Paulo State (CETESB) and the Guidelines for Organic Quality Standard of Instituto Biodinamico (IBD). Concentrations above reference values were found for Co, Cr and Zn in compost, Cr and Zn in cattle manure and Zn in rice bran.

Chemical composition of tomato seeds affected by conventional and organic production systems

Tomato is amongst the most consumed vegetables in the world, not only for its culinary versatility but also for its high nutritional value. In the last years, consumers have shown an increased concern regarding food origin and safety. The organic tomato production has been a promising alternative for the consumer offering a safer food in relation to environmental, social and nutritional aspects. This study assessed the chemical composition of tomato seeds produced in both conventional and organic systems by INAA. The results showed significant differences (P <= 0.05) in the mass fractions of Br, Cs, Eu, Fe, K, Mo, Na, Rb and Sm between both systems, indicating influence of the crop management adopted in the different tomato production systems.

Relevance of leaf surface contamination for assessing chemical composition of bromeliads in a restinga forest

Resuspended soil and other airborne particles adhered to the leaf surface affect the chemical composition of the plant. A well-defined cleaning procedure is necessary to avoid this problem, providing a correct assessment of the inherent chemical composition of bromeliads. To evaluate the influence of a washing procedure, INAA was applied for determining chemical elements in the leaves of bromeliads from Vriesea carinata species, both non-washed and washed with Alconox, EDTA and bi-distilled water. Br, Ce, Hg, La, Sc, Se, Sm and Th showed higher mass fractions in non-washed leaves. The washing procedure removed the exogenous material without leaching chemical elements from inside the tissues.

Atlantic forest: A natural reservoir of chemical elements

The accumulation of chemical elements in biological compartments is one of the strategies of tropical species to adapt to a low-nutrient soil. This study focuses on the Atlantic Forest because of its eco-environmental importance as a natural reservoir of chemical elements. About 20 elements were determined by INAA in leaf, soil, litter and epiphyte compartments. There was no seasonality for chemical element concentrations in leaves, which probably indicated the maintainance of chemical elements in this compartment. Considering the estimated quantities, past deforestation events could have released large amounts of chemical elements to the environment.

Determination of Cr, Fe, Co, Ni, Cu, Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 mu L) was dried on a 6.35 mu m thickness Mylar film at 60 degrees C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from (19)K to (92)U simultaneously.

Assessing sample representativeness for inorganic chemical investigation of invertebrates by INAA

The quality of environmental studies depends on the utilization of adequate sampling protocol and analytical method for obtaining reliable results and minimizing analytical uncertainties. In order to demonstrate the applicability of INAA for determining chemical element composition of invertebrates, this work evaluated sample representativeness in terms of subsampling and sample size. Br, Co, Fe, K, Na, Sc and Zn could be determined in very small samples despite increasing of analytical uncertainties. Special attention should be directed to invertebrate species with small structures because of the high chemical variation observed among different sample sizes tested.