Investigation of Iron (III) desferrioxamine B oxalate ligand exchange by UV-vis spectroscopy: the next step in developing a quantitative analytical method for measuring bioavailable iron in marine ecosystems

To date there are no analytical techniques designed to exclusively measure bioavailable iron in marine environments. The goal of this research is to develop such a technique by isolating the bioavailable iron using the terrestrial siderophore desferrioxamine B (DFB). This project contained many challenging aspects, but the specific goal of this study was to develop a robust analytical technique for quantification of Fe(III)-DFB complexes at nanomolar concentrations. Past work showed that oxalate (Ox) promotes photodissociation of Fe(III)-DFB to Fe(Il), and we are specifically interested in the mechanism of this process. A model was developed using known thermodynamic constants for Fe(III)-DFB and Fe(III) oxalato complexes and adjusting for ionic strength. The model was confirmed by monitoring the UV-VIS absorbance of the system at a variety of oxalate concentrations and pH. The model did not include ternary complexes. Next., the rate of Fe(1I) production during UV irradiation was examined. The results showed that the rate of Fe(II) production was based entirely on the [Fe(Ox)?]3- speciation, and that reoxidation of Fe(II) occurred via reactive oxygen intermediates. This reoxidation could be avoided by either decreasing the oxygen concentration or by adding a Fe(II) stabilizing reagent, such as ferrozine. Further studies need to be done to confirm that these results apply at sub nanomolar concentrations, and the issue of Fe(II) reoxidation at lower Fe concentrations needs to be addressed.

Respostas fisiológicas de diferentes clones de eucalipto sob diferentes regimes de irrigação

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

Effects of chronic acetazolamide administration on gas exchange and acid-base control in pulmonary circulation in exercising horses

P>Reasons for performing study:Carbonic anhydrase (CA) catalyses the hydration/dehydration reaction of CO(2) and increases the rate of Cl- and HCO(3)- exchange between the erythrocytes and plasma. Therefore, chronic inhibition of CA has a potential to attenuate CO(2) output and induce greater metabolic and respiratory acidosis in exercising horses.Objectives:To determine the effects of Carbonic anhydrase inhibition on CO(2) output and ionic exchange between erythrocytes and plasma and their influence on acid-base balance in the pulmonary circulation (across the lung) in exercising horses with and without CA inhibition.Methods:Six horses were exercised to exhaustion on a treadmill without (Con) and with CA inhibition (AczTr). CA inhibition was achieved with administration of acetazolamide (10 mg/kg bwt t.i.d. for 3 days and 30 mg/kg bwt before exercise). Arterial, mixed venous blood and CO(2) output were sampled at rest and during exercise. An integrated physicochemical systems approach was used to describe acid base changes.Results:AczTr decreased the duration of exercise by 45% (P < 0.0001). During the transition from rest to exercise CO(2) output was lower in AczTr (P < 0.0001). Arterial PCO(2) (P < 0.0001; mean +/- s.e. 71 +/- 2 mmHg AczTr, 46 +/- 2 mmHg Con) was higher, whereas hydrogen ion (P = 0.01; 12.8 +/- 0.6 nEq/l AczTr, 15.5 +/- 0.6 nEq/l Con) and bicarbonate (P = 0.007; 5.5 +/- 0.7 mEq/l AczTr, 10.1 +/- 1.3 mEq/l Con) differences across the lung were lower in AczTr compared to Con. No difference was observed in weak electrolytes across the lung. Strong ion difference across the lung was lower in AczTr (P = 0.0003; 4.9 +/- 0.8 mEq AczTr, 7.5 +/- 1.2 mEq Con), which was affected by strong ion changes across the lung with exception of lactate.Conclusions:CO(2) and chloride changes in erythrocytes across the lung seem to be the major contributors to acid-base and ions balance in pulmonary circulation in exercising horses.

Comparative gas exchange performance during the wet season of three Brazilian Styrax species under habitat conditions of cerrado vegetation types differing in soil water availability and crown density

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

Gas exchange and ventilation during dormancy in the tegu lizard Tupinambis merianae

The tegu lizard Tupinambis merianae exhibits an episodic ventilatory pattern when dormant at 17 degrees C but a uniform ventilatory pattern when dormant at 25 degrees C. At 17 degrees C, ventilatory episodes were composed of 1-22 breaths interspaced by non-ventilatory periods lasting 1.8-26min, Dormancy at the higher body temperature was accompanied by higher rates of O-2 consumption and ventilation. The increase in ventilation was due only to increases in breathing frequency with no change observed in tidal volume. The air convection requirement for O-2 did not differ at the two body temperatures. The respiratory quotient was 0.8 at 17 degrees C and 1.0 at 25 degrees C. We found no consistent relationship between expired gas composition and the start/end of the ventilatory period during episodic breathing at 17 degrees C. However, following non-ventilatory periods of increasing duration, there was an increase in the pulmonary O-2 extraction that was not coupled to an equivalent increase in elimination of CO2 from the lungs. None of the changes in the variables studied could alone explain the initiation/termination of episodic ventilation in the tegus, suggesting that breathing episodes are shaped by a complex interaction between many variables. The estimated oxidative cost of breathing in dormant tegus at 17 degrees C was equivalent to 52.3% of the total metabolic rate, indicating that breathing is the most costly activity during dormancy.

Anodic Stripping Voltammetric Determination of Lead (II) and Cadmium (II) by Using a Carbon Nanotubes Paste Electrode Modified with Ion Exchange Synthetic Resin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Spin reversal and magnetization jumps in ErMexMn1-xO3 perovskites (Me = Ni, Co)

The erbium-based manganite ErMnO3 has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni) = 0.2-0.5 in the nickel-based solid solution ErNixMn1-xO3, while it can be extended up to x(Co) = 0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co3+. Presence of different magnetic entities (i.e., Er3+, Ni2+, Co2+, Co3+, Mn3+, and Mn4+) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNixMn1-xO3, a critical concentration x(crit)(Ni) = 1/3 separates two regimes: spin-canted AF interactions predominate at x < x(crit), while the ferromagnetic behavior is enhanced for x > x(crit). Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at T-c, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T-1, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo0.50Mn0.50O3 was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50 = Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co2+ and Co3+ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate. (C) 2006 Elsevier B.V. All rights reserved.

A new approach for determining stability constants of metal ion complexes in aquatic systems based on flow injection-ion exchange-flame atomic absorption spectrometry coupling

A method based an ion exchange(IE)-atomic absorption spectrometry(AAS) coupled by flow techniques, allowing the determination of formation constants of, at least, the first species of complex systems, in aqueous solution, was developed.The IE-AAS coupling reduces significantly the number of experimental steps in comparison with IE batch methods, resulting in an important increase in analytical rate. The method is simple both from experimental and computational points of view, making possible its utilization by workers without special expertise in the field of complex equilibria in solution. on the other hand, taking into account mainly the amount of hollow cathode lamps available to date, the developed procedure may be applied, within certain limitations, to the study of many systems whose features prevent the use of traditional approaches.

Influence of biosolids rate on chemical properties of an oxisol in São Paulo, Brazil

Organic residues may cause major health and environmental problems. This is the case in our study area, where more than 10 billion L per year of residential and industrial waste are produced. Land application of biosolids can be an economical solution by recycling waste and can provide valuable fertilizer if used correctly. The aim of this work was to study the effect of biosolids on the chemical properties of an Oxisol. The experiment was located at Ilha Solteira northwest of São Paulo State, Brazil. The soil was cropped to Sorghum bicolor.The field experimental design consisted of random blocks with six treatments and four replications of each treatment. Biosolids were surface applied to four treatments at rates of 5, 10, 20, and 40 Mg ha(-1) on a dry matter basis; in addition, a treatment with mineral fertilizer and a control were included. One year after biosolids application, soil samples were taken at 0-10, 10-20, and 20-40 cm. Organic matter content (Walkley-Black) and pH (CaCl2) were routinely determined. Cation exchange capacity, exchangeable bases (Ca, Mg, K), and P were determined by exchange resin extraction. No significant differences in any of the analyzed properties were found below the 20 cm depth. Extractable phosphorus (P) and potassium (K) increased with increasing biosolids rate in the top 20 cm, whereas calcium (Ca) and (Ma) magnesium content were not significantly influenced by biosolids. Soil pH decreased with increasing biosolids application. The sewage sludge application did not influence the sorghum production in the first year of culture, under unfavorable soil moisture conditions, but it influenced the dry matter.

Irradiance stress responses of gas exchange and antioxidant enzyme contents in pariparoba [Pothomorphe umbellata (L.) Miq.] plants

We evaluated the growth and development of the medicinal species Pothomorphe umbellata ( L.) Miq. under different shade levels ( full sun and 30, 50, and 70 % shade, marked as I(100), I(70), I(50), and I(30), respectively) and their effects on gas exchange and activities of antioxidant enzymes. Photosynthetically active radiation varied from 1 254 mu mol m(-2) s(-1) at I(100) to 285 mu mol m(-2) s(-1) at I(30). Stomatal conductance, net photosynthetic rate, and relative chlorophyll (Chl) content were maximal in I(70) plants. Plants grown under I(100) produced leaves with lower Chl content and signs of chlorosis and necrosis. These symptoms indicated Chl degradation induced by the generation of reactive oxygen species. Stress related antioxidant enzyme activities ( Mn-SOD, Fe-SOD, and Cu/Zn-SOD) were highest in I(100) plants, whereas catalase activity was the lowest. Hence P. umbellata is a shade species ( sciophyte), a feature that should be considered in reforestation programs or in field plantings for production of medicinal constituents.

Micellar modification of drug stability: analysis of the effect of hexadecyltrimethylammonium halides on the rate of degradation of cephaclor

The intra- and intermolecular rates of degradation of cephaclor were determined with and without hexadecyltrimethylammonium bromide (CTABr). Micellar-derived spectral shifts were used to measure the association of the ionic forms as well as to determine the effect of CTABr on the apparent acid dissociation constant of the antibiotic. The rate of degradation of cephaclor increased with detergent and was salt sensitive. Micellar effects were analyzed quantitatively within the frame-work of the speudophase ion exchange model. All experimental data were fitted to this model which was used to predict the combined effects of pH and detergent concentration. Micelles increased the rate of OH- attack on cephaclor; most of the effect was due to the concentration of reagents in the micellar pseudophase. The intramolecular degradation was catalyzed 25-fold by micelles, and a working hypothesis to rationalize this effect is proposed. The results demonstrate that quantitative analysis can be utilized to assess and predict effects of detergents on drug stability.

Effects of soil water deficit and nitrogen nutrition on water relations and photosynthesis of pot-grown Coffea canephora Pierre

Coffea canephora plants (clone INCAPER-99) were submitted to low N (LN) or high N (HN) applications and two watering regimes (daily irrigation and irrigation every 5 days for a month). Although water potential was not altered significantly by N, HN plants showed higher relative water content than did LN plants under water deficit. Only HN plants exhibited some ability for osmotic adjustment. Plants from both N treatments increased their cell wall rigidity under drought, with a more pronounced augmentation in HN plants. In well-watered plants, carbon assimilation rate increased with increasing N while stomatal conductance did not respond to N supply. Under drought conditions, carbon assimilation decreased by 68-80% compared to well-watered plants, whereas stomatal conductance and transpiration rate declined by 35% irrespective of the N applications. Stable carbon isotope analysis, combined with leaf gas exchange measurements, indicated that regardless of the watering treatments, N increased the long-term water use efficiency through changes in carbon assimilation with little or no effect on stomatal behaviour.

A method for improving the code rate and error correction capability of a cyclic code

Currently, there has been an increasing demand for operational and trustworthy digital data transmission and storage systems. This demand has been augmented by the appearance of large-scale, high-speed data networks for the exchange, processing and storage of digital information in the different spheres. In this paper, we explore a way to achieve this goal. For given positive integers n,r, we establish that corresponding to a binary cyclic code C0[n,n-r], there is a binary cyclic code C[(n+1)3k-1,(n+1)3k-1-3kr], where k is a nonnegative integer, which plays a role in enhancing code rate and error correction capability. In the given scheme, the new code C is in fact responsible to carry data transmitted by C0. Consequently, a codeword of the code C0 can be encoded by the generator matrix of C and therefore this arrangement for transferring data offers a safe and swift mode. © 2013 SBMAC - Sociedade Brasileira de Matemática Aplicada e Computacional.

Alterações bioquímicas, morfofisiológicas e produtivas em genótipos de arroz em dois regimes hídricos

Pós-graduação em Agronomia (Agricultura) - FCA

Híbridos de eucalipto sob diferentes regimes hídricos em vasos e crescimento no campo

Pós-graduação em Agronomia (Genética e Melhoramento de Plantas) - FCAV