Magnetoelectric effects in an organometallic quantum magnet

Metal-organic materials constitute a new field in which to search for ferroelectricity and coupling between electricity and magnetism. We observe a magnetic field-induced change in the electric polarization, Delta P(H), that reaches 50 mu C/m(2) in single crystals of NiCl(2)-4SC(NH(2))(2) (DTN). DTN forms a tetragonal structure that breaks inversion symmetry with the electrically polar thiourea molecules [SC(NH(2))] all tilted in the same direction along the c axis. The field H induces canted antiferromagnetism of the Ni S = 1 spins between 2 and 12 T and our measurements show that the electric polarization increases monotonically in this range, saturating above 12 T. By modeling the microscopic origin of this magnetoelectric effect, we find that the leading contribution to Delta P comes from the change in the crystal electric field, with a smaller contribution from magnetic exchange striction. The finite value of Delta P induced by magnetostriction results from the polar nature of the thiourea molecules bonded to the Ni atoms, and it is amplified by the softness of these organic molecules.

Cloud point extraction to avoid interferences by structured background on nickel determination in plant materials by FAAS

An analytical procedure based on microwave-assisted digestion with diluted acid and a double cloud point extraction is proposed for nickel determination in plant materials by flame atomic absorption spectrometry. Extraction in micellar medium was successfully applied for sample clean up, aiming to remove organic species containing phosphorous that caused spectral interferences by structured background attributed to the formation of PO species in the flame. Cloud point extraction of nickel complexes formed with 1,2-thiazolylazo-2-naphthol was explored for pre-concentration, with enrichment factor estimated as 30, detection limit of 5 mu g L(-1) (99.7% confidence level) and linear response up to 80 mu g L(-1). The accuracy of the procedure was evaluated by nickel determinations in reference materials and the results agreed with the certified values at the 95% confidence level.

Highly Toxic Microcystis aeruginosa Strain, Isolated from So Paulo-Brazil, Produce Hepatotoxins and Paralytic Shellfish Poison Neurotoxins

While evaluating several laboratory-cultured cyanobacteria strains for the presence of paralytic shellfish poison neurotoxins, the hydrophilic extract of Microcystis aeruginosa strain SPC777-isolated from Billings`s reservoir, So Paulo, Brazil-was found to exhibit lethal neurotoxic effect in mouse bioassay. The in vivo test showed symptoms that unambiguously were those produced by PSP. In order to identify the presence of neurotoxins, cells were lyophilized, and the extracts were analyzed by HPLC-FLD and HPLC-MS. HPLC-FLD analysis revealed four main Gonyautoxins: GTX4(47.6%), GTX2(29.5%), GTX1(21.9%), and GTX3(1.0%). HPLC-MS analysis, on other hand, confirmed both epimers, with positive Zwitterions M(+) 395.9 m/z for GTX3/GTX2 and M(+) 411 m/z for GTX4/GTX1 epimers. The hepatotoxins (Microcystins) were also evaluated by ELISA and HPLC-MS analyses. Positive immunoreaction was observed by ELISA assay. Alongside, the HPLC-MS analyses revealed the presence of [l-ser(7)] MCYST-RR. The N-methyltransferase (NMT) domain of the microcystin synthetase gene mcyA was chosen as the target sequence to detect the presence of the mcy gene cluster. PCR amplification of the NMT domain, using the genomic DNA of the SPC777 strain and the MSF/MSR primer set, resulted in the expected 1,369 bp product. The phylogenetic analyses grouped the NMT sequence with the NMT sequences of other known Microcystis with high bootstrap support. The taxonomical position of M. aeruginosa SPC777 was confirmed by a detailed morphological description and a phylogenetic analysis of 16S rRNA gene sequence. Therefore, co-production of PSP neurotoxins and microcystins by an isolated M. aeruginosa strain is hereby reported for the first time.

Exploiting Mn(III)/EDTA complex in a flow system with solenoid micro-pumps coupled to long pathlength spectrophotometry for fast manganese determination

The formation of the Mn(III)/EDTA complex in a flow system with solenoid micro-pumps was exploited for fast manganese determination in freshwater. Manganese(II) was oxidized in a solid-phase reactor containing lead dioxide immobilized on polyester. Long pathlength spectrophotometry was exploited to increase sensitivity, aiming to reach the threshold limit established by environmental legislation. A linear response was observed from 25 to 1500 mu g L(-1), with a detection limit of 6 mu g L(-1) (99.7% confidence level). Sample throughput and coefficient of variation were 36 samples/h and 2.6% (n = 10), respectively. EDTA consumption and waste generation were estimated as 500 mu g and 3 mL per determination, respectively. The amount of Pb in the residue corresponds to 250 mu g per determination and a solid-phase reactor could be used for up to 1600 determinations. Adsorption in active charcoal avoided interferences caused by organic matter and the developed procedure was successfully applied for determination of manganese in freshwater samples. Results were in agreement with those attained by GFAAS at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

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.

Coconut coir as biosorbent for Cr(VI) removal from laboratory wastewater

A high cost-effective treatment of sulphochromic waste is proposed employing a raw coconut coir as biosorbent for Cr(VI) removal. The ideal pH and sorption kinetic, sorption capacities, and sorption sites were the studied biosorbent parameters. After testing five different isotherm models with standard solutions, Redlich-Peterson and Toth best fitted the experimental data, obtaining a theoretical Cr(VI) sorption capacity (SC) of 6.3 mg g(-1). Acid-base potentiometric titration indicated around of 73% of sorption sites were from phenolic compounds, probably lignin. Differences between sorption sites in the coconut coir before and after Cr adsorption identified from Fourier transform infrared spectra suggested a modification of sorption sites after sulphochromic waste treatment, indicating that the sorption mechanism involves organic matter oxidation and chromium uptake. For sulphocromic waste treatment, the SC was improved to 26.8 +/- 0.2 mg g(-1), and no adsorbed Cr(VI) was reduced, remaining only Cr(III) in the final solution. The adsorbed material was calcinated to obtain Cr2O3, with a reduction of more than 60% of the original mass. (c) 2008 Elsevier B.V. All rights reserved.

Structure of a Population of Hydromedusa maximiliani (Testudines, Chelidae) from Parque Estadual da Serra do Mar, an Atlantic Rainforest Preserve in Southeastern Brazil

We studied the structure of a population of Hydromedusa maximiliani associated with a stream in Parque Estadual da Serra do Mar, Nucleo Itutinga-Piloes, southeastern Brazil, between October 2004 and October 2005. Twenty-five individuals were captured, and a population size of 43.72 +/- 23.7 individuals was estimated. This value is similar to that of the population of Parque Estadual Carlos Botelho, another Atlantic forest reserve of southeastern Brazil. Males were recaptured more frequently than females, suggesting higher activity and/or greater movement of males.

Yield loss caused by huanglongbing in different sweet orange cultivars in So Paulo, Brazil

Citrus huanglongbing (HLB) reduces an affected orchard`s economic life. This work aimed to characterize yield loss due to HLB for different sweet orange cultivars and determine the relationship between disease severity and yield. Disease severity and yield were assessed on 949 individual trees distributed in 11 different blocks from sweet orange cultivars Hamlin, Westin, Pera and Valencia. In each block, plants showing a range of HLB severity levels and asymptomatic plants were selected. Total yield (weight of harvested fruit), mean weight of asymptomatic and symptomatic fruit, relative yield (symptomatic tree yield/mean yield of asymptomatic trees from the same block) and relative number of fruits (fruit number from symptomatic tree/mean number of fruits from asymptomatic trees from the same block) were determined. The weight of symptomatic fruit was lower than the weight of asymptomatic fruit, but the weights of asymptomatic and symptomatic fruit were not correlated with disease severity, indicating that the effects of HLB were restricted to symptomatic branches. The relationship of the relative yield with HLB severity can be satisfactorily described by a negative exponential model. The rates of yield decrease as a function of disease severity were similar for all assessed cultivars. A relative yield (up to 19%) was observed even for trees where disease severity was 100%. The strong linear relationship between relative number of fruits per tree and the relative yield per tree suggested that the yield reduction was due primarily to early fruit drop or lack of fruit set on affected branches.

Genetic potential of a maize population from Southern Brazil for the modified convergent-divergent selection scheme

Maize (Zea mays L.) is a very important cereal to world-wide economy which is also true for Brazil, particularly in the South region. Grain yield and plant height have been chosen as important criteria by breeders and farmers from Santa Catarina State (SC), Brazil. The objective of this work was to estimate genetic-statistic parameters associated with genetic gain for grain yield and plant height, in the first cycle of convergent-divergent half-sib selection in a maize population (MPA1) cultivated by farmers within the municipality of Anchieta (SC). Three experiments were carried out in different small farms at Anchieta using low external agronomic inputs; each experiment represented independent samples of half-sib families, which were evaluated in randomized complete blocks with three replications per location. Significant differences among half-sib families were observed for both variables in all experiments. The expected responses to truncated selection of the 25% better families in each experiment were 5.1, 5.8 and 5.2% for reducing plant height and 3.9, 5.7 and 5.0% for increasing grain yield, respectively. The magnitudes of genetic-statistic parameters estimated evidenced that the composite population MPA1 exhibits enough genetic variability to be used in cyclical process of recurrent selection. There were evidences that the genetic structure of the base population MPA1, as indicated by its genetic variability, may lead to expressive changes in the traits under selection, even under low selection pressure.

Natural regeneration of Atlantic Forest species in the understory of Eucalyptus saligna Smith. in a former forest production unit at the Parque das Neblinas, Bertioga, SP

This study aimed at characterizing the potential for natural regeneration of native vegetation in the under-story of an earlier Eucalyptus saligna Smith production stand. The study was carried out at the Parque das Neblinas, Bertioga municipality, SP, in a 45 ha third rotation stand; which had been abandoned 15 years ago for natural regeneration to occur. The sampling was done in 24 plots of 20 x 40 m. The sampled area was of 19,200 m(2), with inventory made of 100% of the eucalyptus trees. All regeneration trees with a height >= 1.30 m and DBH >= 5.0 cm were measured, as well as adult individuals with DBH >= 5.0 cm; surveyed in two size classes. 1,417 individuals of E. saligna were measured, with a density of 738,02 individuals/ha and a basal area of 22.69 m(2)/ha. Among 2,763 natural regeneration individuals, 111 species belonged to 66 genera and 34 botanical families. The species represented 43.7% of the tree richness of neighboring native forest fragments. The total estimated density and the basal area were respectively 1,052.6 individuals/ha and 6.4 m(2)/ha of autochthonous trees with DBH >= 5.0 cm (Class 1); while for regeneration there were 3,864.58 individuals/ha, and 2.76 m(2)/ha of individuals with a height >= 1.30 m and DBH <5.0 cm (Class 2). Shannon diversity (H`) was 2.83 and 3.68, respectively, for Classes 1 and 2, and the corrected species richness for a 1000-individual sample (R(1000)) were 75.6 and 87.29 (Fisher`s a index) for the same classes. The majority of the species (34.84%) was typical from the understory of wet tropical forest and had zoochoric fruit dispersal (67.57%). The results indicate that, under these conditions, a eucalyptus forest is able to provide adequate regeneration niches for native vegetation, and may represent a sink habitat for local populations.

Phenolic composition and antioxidant activity of culms and sugarcane (Saccharum officinarum L.) products

The present work reports amounts of flavonoids and phenylpropanoids of culms of three sugarcane varieties and of raw juice, syrup, molasse and VHP sugar. The antioxidant activity of those materials was evaluated by the DPPH and beta-carotene/linoleic acid methods. The predominant phenolics in culms were phenylpropanoids (caffeic, chlorogenic and coumaric acids), while flavones (apigenin, tricin and luteolin derivatives) appeared in lower amounts. Differences were noted either among phenolic profiles of sugarcane culms or between culms and sugarcane products. The antioxidant activities of solutions from most samples were similar or higher than a 80 mu M Trolox solution. (C) 2010 Elsevier Ltd All rights reserved.

An Apparent Paradox: Attenuation of Phenylephrine-mediated Calcium Mobilization and Hyperreactivity to Phenylephrine in Contralateral Carotid After Balloon Injury

Balloon catheter injury promotes hyperreactivity to phenylephrine (Phe) in the contralateral carotid. Phe-induced contraction involves calcium mobilization, a process that may be sensitive to reactive oxygen species. In this study, we investigated whether increased reactivity to Phe in the contralateral carotid is due to alterations in calcium mobilization by Phe and reactive oxygen species signaling. Concentration-response curves to Phe were obtained in control and contralateral arteries 4 days after balloon injury. Tiron did not modify E(max) to Phe in control arteries but reduced this parameter in the contralateral carotid to control levels. Moreover, immunofluorescence to dihydroethydine showed increased basal oxidative stress in the contralateral artery compared with control artery. Intracellular calcium mobilization by Phe in the contralateral artery was not different from control, but Phe-induced extracellular calcium mobilization was reduced in the contralateral artery compared with that in the control. These data were confirmed by confocal microscopy using Fluo 3-AM. Tiron and SC-236 increased Phe-induced calcium influx in the contralateral artery, which was similar to controls in the same conditions. However, catalase did not modify this response. Taken together, our results suggest that superoxide anions and prostanoids from cyclooxygenase-2 alter pathways downstream of alpha(1)-adrenoceptor activation in the contralateral carotid in response to injury. This results in reduced Phe-induced calcium influx, despite hyperreactivity to Phe.

Preparation and characterization of chitosan-treated alginate microparticles incorporating all-trans retinoic acid

Chitosan treated alginate microparticles were prepared with the purpose of incorporating all-trans retinoic acid (ATRA) using an inexpensive, simple and fast method, enhancing dermal localization and sustaining the release of ATRA into the skin. Microparticles characterization, drug-polymer interaction, release profile and in vitro skin retention were investigated. Microparticles presented spherical shape and drug loading capacity of 47%. The drug content of these microparticles was affected by ATRA concentration and by the solvent used and it was more weakly affected by chitosan concentration. The release of ATRA was also affected by chitosan concentration. Microparticles prepared with 0.4% chitosan (w/w) resulted in drug release with a more sustained profile. The results of in vitro retention studies showed that chitosan treated alginate microparticles decreased the drug retention in the stratum corneum (SC), where occur the skin irritation, but maintained the ATRA concentration in the deeper skin layers, where occur the pathologies treated with ATRA. Then, the microparticles developed in this work can be a good candidate to improve the topical therapy with retinoid.

Development and validation of HPLC method for imiquimod determination in skin penetration studies

A simple, rapid and sensitive analytical procedure for the measurement of imiquimod in skin samples after in vitro penetration studies has been developed and validated. In vitro penetration studies were carried out in Franz diffusion cells with porcine skin. Tape stripping technique was used to separate the stratum corneum (SC) from the viable epidermis and dermis. Imiquimod was extracted from skin samples using a 7:3 (v/v) methanol:acetate buffer (100 mm, pH 4.0) solution and ultrasonication. Imiquimod was analyzed by H-PLC using C(8) column and UV detection at 242 ran. The mobile phase used was acetonitrile:acetate buffer (pH 4.0, 100 mM):diethylamine (30:69.85:0.15, v/v) with flow rate 1 mL/min. Imiquimod eluted at 4.1 min and the running time was limited to 6.0 min. The procedure was linear across the following concentration ranges: 100-2500 ng/mL for both SC and tape-stripped skin and 20-800 ng/mL for receptor solution. Intra-day and inter-day accuracy and precision values were lower than 20% at the limit of quantitation. The recovery values ranged from 80 to 100%. The method is adequate to assay imiquimod from skin samples, enabling the determination of the cutaneous penetration profile of uniquimod by in vitro studies. Copyright (C) 2008 John Wiley & Sons, Ltd.

Iontophoretic transport of zinc phthalocyanine tetrasulfonic acid as a tool to improve drug topical delivery

Phthalocyanines have been used as systemic photosensitizers because of their high affinity towards tumour tissue, and the high rates of reactive oxygen species produced when they are irradiated during photodynamic therapy. However, the topical administration of these compounds is limited by their large size, poor hydrosolubility and ionic character. This study aimed to investigate the iontophoretic delivery of charged zinc phthalocyanine tetrasulfonic acid (ZnPcS(4)) from a hydrophilic gel to different skin layers by means of in-vitro and in-vivo studies. Six hours of passive administration was insufficient for ZnPcS(4) to cross the stratum corneum (SC) and to reach the epidermis and dermis. No positive effect was reached when anodal iontophoresis was performed, showing that the drug-electrode attraction effect was higher than the electro-osmosis contribution at a pH of 5.5. Cathodal iontophoresis, however, was able to transport significant amounts of the drug to the viable epidermis. In addition, the absence of NaCl in the formulation significantly increased (by five-fold) the amount of ZnPcS(4) that crossed the SC and accumulated in the epidermis and dermis. It was possible to visualize the drug accumulation in the follicle openings and in the epidermis, even after SC removal. In-vivo experiments in rat skin showed that these results were maintained in an in-vivo model, even with only 15 min of iontophoresis. In addition, confocal analysis of the treated skin showed a homogeneous distribution of ZnPcS(4) in the viable epidermis after this short period of cathodal iontophoresis. Anti-Cancer Drugs 22:783-793 (C) 2011 Wolters Kluwer Health | Lippincott Williams & Wilkins.