Probing the binding of tetraplatinum(pyridyl)porphyrin complexes to DNA by means of surface plasmon resonance

Tetrapyridylporphyrins containing four chloro(2,2`-bipyridine)platinum(II) complexes attached at the meta (3-H(2)TPtPyP) and para (4-H(2)TPtPyP) positions of the peripheral pyridine ligands were synthesized and their interaction with DNA investigated. The compounds were isolated in the solid state and characterized by means of spectroscopic and analytical techniques. According to molecular simulations, the two isomers exhibit contrasting structural characteristics, consistent with a saddle shape configuration for 3-H(2)TPtPyP and a planar geometry for 4-H(2)TPtPyP. Surface plasmon resonance studies were carried out on the interaction of the complexes with calf thymus DNA, revealing a preferential binding of 3-H(2)TPtPyP, presumably at the DNA major grooves. (C) 2008 Elsevier Inc. All rights reserved.

Trace element impurity determination in aspirin tablets by INAA

Instrumental neutron activation analysis (INAA) was applied to assess trace element concentrations in six samples of aspirin tablets acquired in SA o pound Paulo city, Brazil. Concentrations of the elements Br, Ca, Co, Cr, Fe, K, La, Na, Sc and Zn were determined. Comparisons were made between the results obtained with published data for aspirins from foreign countries. Certified reference materials, INCT-MPH-2 Mixed Polish Herbs were analyzed for quality control of the analytical results.

Development of a sensitive passive sampler using indigotrisulfonate for the determination of tropospheric ozone

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The application of biochemical responses to assess environmental quality of tropical estuaries: field surveys

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Assessment of metal and trace element concentrations in the Cananeia estuary, Brazil, by neutron activation and atomic absorption techniques

Twenty six bottom sediment samples were collected from the Cananeia estuary in summer and winter of 2005. Multielemental analysis was carried out by instrumental neutron activation analysis. Total mercury was determined by cold vapor atomic absorption. As, Cr, Hg and Zn concentrations were compared to the Canadian oriented values (TEL and PEL). Sample points 4 and 9 presented higher concentration for most elements and As and Cr exceeded the TEL values. Organic matter (>10%) associated with siltic and clay sediments was observed. Climatic conditions, hydrodynamic and biogeochemical processes promote differences in seasonal concentrations of elements at some points, which contribute to special distributions.

Effects of extrusion, lipid concentration and purity on physico-chemical and biological properties of cationic liposomes for gene vaccine applications

We developed cationic liposomes containing DNA through a conventional process involving steps of (i) preformation of liposomes, (ii) extrusion, (iii) drying and rehydration and (iv) DNA complexation. Owing to its high prophylactic potentiality against tuberculosis, which had already been demonstrated in preclinical assays, we introduced modifications into the conventional process towards getting a simpler and more economical process for further scale-up. Elimination of the extrusion step, increasing the lipid concentration (from 16 to 64 mM) of the preformed liposomes and using good manufacturing practice bulk lipids (96-98% purity) instead of analytical grade purity lipids (99.9-100%) were the modifications studied. The differences in the physico-chemical properties, such as average diameter, zeta potential, melting point and morphology of the liposomes prepared through the modified process, were not as significant for the biological properties, such as DNA loading on the cationic liposomes, and effective immune response in mice after immunisation as the control liposomes prepared through the conventional process. Beneficially, the modified process increased productivity by 22% and reduced the cost of raw material by 75%.

Further investigating the determination of phosphorus in plants by INAA using bremsstrahlung measurement

Phosphorus is an essential element for plants and animals, playing a fundamental role in the production of biochemical energy. Despite its relevance, phosphorus is not commonly determined by instrumental neutron activation analysis (INAA), because (32)P does not emit gamma-rays in its decay. There are alternative methods for the determination of phosphorus by INAA, such as the use of beta counting or the measurement of bremsstrahlung originated from the high energy beta particle from (32)P. Here the determination of phosphorus in plant materials by measuring the bremsstrahlung production was further investigated, to optimize an analytical protocol for minimizing interferences and overcoming the poor specificity. Eight certified reference materials of plant matrices with phosphorus ranging between 171 and 5,180 mg kg(-1) were irradiated at a thermal neutron flux of 9.5 x 10(12) cm(-2) s(-1) and measured with a HPGe detector at decay times varying from 7 to 60 days. Phosphorus solutions added to a certified reference material at three levels were used for calibration. Counts accumulated in the baseline at four different regions of the gamma-ray spectra were tested for the determination of phosphorus, with better results for the 100 keV region. The Compton scattering contribution in the selected range was discounted using an experimental peak-to-Compton factor and the net areas of all peaks in the spectra with energies higher than 218 keV, i.e. Compton edge above 100 keV. Amongst the interferences investigated, the production of (32)P from sulfur, and the contribution of Compton scattering should be considered for producing good results.

Bioaccumulation pattern of lanthanides in pteridophytes and magnoliophytes species from Atlantic Forest

The availability of chemical elements for plants is mainly dependent on the nature of the soil and characteristics of each species. The transfer factors of lanthanides from the soil to the tree leaves of the Atlantic Forest, Brazil, were calculated for one fern species (Alsophila sternbergii-Pteridophyta division) and four magnoliophytes species (Bathysa australis, Euterpe edulis, Garcinia gardneriana and Guapira opposita-Magnoliophyta division) obtained in two areas of Serra do Mar State Park and collected in two different seasons. Samples were analyzed by instrumental neutron activation analysis (INAA). The soil-to-plant transfer factor (TF = C(plant):C(soil)) in magnoliophytes species was correlated to the mass fraction of lanthanides in the soil, described by a exponential model (TF = a.C (soil) (-b) ). Despite the tree fern Alsophila sternbergii presented a hyperaccumulation of lanthanides, this species did not have a significant relationship between TF and mass fraction in soil. Results indicated that plants of Magnoliophyta division selected the input of lanthanides from the soil, while the same was not observed in Alsophila sternbergii.

Biomonitoring of coastal regions of So Paulo State, Brazil, using mussels Perna perna

The marine environment is constantly affected by anthropic actions, with causes consequent degradation of the waters and marine biota by various discharges of xenobiotics. In the present study, the focus was the study of a region of the marine coast of the State of So Paulo (city of Santos), which is one of the most industrialized parts of Brazil and suffers also from a strong impact of domestic effluents. The mussel Perna perna, very abundant in the coast of the State of So Paulo, Brazil, was selected as the biomonitoring organism for the determination of inorganic elements and a passive biomonitoring was performed. The organisms were collected at two sites in So Paulo State coast: Cocanha beach in Caraguatatuba (mussel farm) and Santos Bay (Itaipu and Palmas). Seasonally, the Perna perna were collected between September/08 and July/09 in each study sites. After removal and sample preparation, the elements As, Co, Cr, Fe, Se and Zn were determined by instrumental neutron activation analysis (INAA) and Cd, Pb and Hg were determined by atomic absorption spectroscopy (AAS) in this organism.

Elemental composition evaluation in lichens collected in the industrial city of So Mateus Sul, Parana, Brazil

In this study, Canoparmelia texana lichenized fungi species was used as a passive biomonitor of the atmospheric pollution from the industrial city of So Mateus do Sul, PR, Brazil. Lichen samples collected from tree barks were cleaned, freeze-dried and analyzed by neutron activation analysis. Comparisons were made between the element concentrations obtained in lichens from this city and that from a clean area of Atlantic Forest in Intervales Park, SP. The high concentrations of elements As, Ca, Co, Cr, Fe, Hf, Sb, and Th found in lichens could be attributed to the emissions from a ceramic and an oil shale plants.

Comparison of INAA elemental composition data between Lago Grande and Osvaldo archaeological sites in the central Amazon: a first perspective

In this work, 50 ceramic fragments from the Lago Grande and 30 from the Osvaldo archaeological site were compared to assess elemental similarities. The aim is to perform a preliminary comparison between the sites, which are located in the central Amazon, Brazil. The analytical technique employed to obtain the ceramics elemental composition was instrumental neutron activation analysis (INAA). The data set obtained was explored by the multivariate statistical techniques of cluster, principal component and discriminant analysis. The analyzed elements were: Na, Lu, U, Yb, La, Th, Cr, Cs, Sc, Fe, Eu, Ce and Hf. The results showed the existence of at least two compositional groups for Lago Grande and Osvaldo. Each compositional group of Osvaldo archaeological site matches with one group of Lago Grande. Correlated with the archaeological background, the results suggest commercial or cultural exchange in the region, which is an indicative of socio-cultural interactions between those sites.

Vanadium biomonitoring by using Perna perna (Linnaeus, 1758) mussels transplanted in the coast of the State of So Paulo, Brazil

The increased pollution in the aquatic ecosystem has led to the investigation of toxic elements in sea water by using marine organisms to assess marine pollution from human activities. Among these organisms, the mollusks bivalves have been used as biomonitors since they can accumulate trace elements and other substances, without the occurrence of their death. In this study, Perna perna mussels were transplanted from a mussel farm (reference region) to four sites located in coastal regions of So Paulo State, Brazil, close to anthropic discharge areas. Vanadium was determined in mussel tissues by instrumental neutron activation analysis (INAA). Quality control of V analysis was checked by analyzing biological reference materials and the results obtained were precise and in good agreement with the certified values. Comparisons between the V concentrations obtained in transplanted mussels indicated that those from So Sebastio region, close to an oil terminal presented the highest concentration of this element, during spring.

K-41(n, gamma)K-42 thermal and resonance integral cross section measurements

We measured the K-41 thermal neutron absorption and resonance integral cross sections after the irradiation of KNO3 samples near the core of the IEA-R1 IPEN pool-type research reactor. Bare and cadmium-covered targets were irradiated in pairs with Au-Al alloy flux-monitors. The residual activities were measured by gamma-ray spectroscopy with a HPGe detector, with special care to avoid the K-42 decay beta(-) emission effects on the spectra. The gamma-ray self-absorption was corrected with the help of MCNP simulations. We applied the Westcott formalism in the average neutron flux determination and calculated the depression coefficients for thermal and epithermal neutrons due to the sample thickness with analytical approximations. We obtained 1.57(4) and 1.02(4) b, for thermal and resonance integral cross sections, respectively, with correlation coefficient equal to 0.39.

Neutron activation analysis for assessing chemical composition of dry dog foods

Brazil holds the second largest population of domestic dogs in the world, with 33 million dogs, only behind the United States. The annual consumption of dog food in the country is 1.75 million tons, corresponding to the World's sixth in trade turnover. Dog food is supposed to be a complete and balanced diet, formulated with high quality ingredients. All nutrients and minerals required for an adequate nutrition of dogs are added to the formulation to ensure longevity and welfare. In this context, the present study aimed at assessing the chemical composition of dry dog foods commercialized in Brazil. Thirty-four samples were acquired in the local market of Piracicaba and analyzed by instrumental neutron activation analysis (INAA) to determine the elements As, Br, Ca, Co, Cr, Cs, Fe, K, La, Na, Rb, Sb, Sc, Se, U, and Zn. In general, the concentrations of Ca, Fe, K, Na, and Zn complied with the values required by the Association of American Feed Control Officials (AAFCO). To evaluate the safety of dog food commercialized in Brazil, further investigation is necessary to better understand the presence of toxic elements found in this study, i.e. Sb and U. INAA was useful for the screening analysis of different types and brands of dry dog foods for the determination of both essential and toxic elements.

Assessment and optimization of chemical industrial processes from a life cycle perspective

During the PhD program in chemistry, curriculum in environmental chemistry, at the University of Bologna the sustainability of industry was investigated through the application of the LCA methodology. The efforts were focused on the chemical sector in order to investigate reactions dealing with the Green Chemistry and Green Engineering principles, evaluating their sustainability in comparison with traditional pathways by a life cycle perspective. The environmental benefits associated with a reduction in the synthesis steps and the use of renewable feedstock were assessed through a holistic approach selecting two case studies with high relevance from an industrial point of view: the synthesis of acrylonitrile and the production of acrolein. The current approach wants to represent a standardized application of LCA methodology to the chemical sector, which could be extended to several case studies, and also an improvement of the current databases, since the lack of data to fill the inventories of the chemical productions represent a huge limitation, difficult to overcome and that can affects negatively the results of the studies. Results emerged from the analyses confirms that the sustainability in the chemical sector should be evaluated from a cradle-to-gate approach, considering all the stages and flows involved in each pathways in order to avoid shifting the environmental burdens from a steps to another. Moreover, if possible, LCA should be supported by other tools able to investigate the other two dimensions of sustainability represented by the social and economic issues.