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.

Determination of sodium oxalate in Bayer process liquors using flow analysis with tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection

The research was a detailed investigation into a challenging analytical chemistry problem for the alumina industry. The successful outcomes were derived through innovative reagent chemistry and novel instrumental development. The resultant methodology and instrumentation deployed on this most demanding sample matrix is more robust, reliable and less expensive than anything currently used in this industry worldwide.

Luminescent and morphological study of Sr2CeO4 blue phosphor prepared from oxalate precursors

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

Role of intermediary cells in Peltodon radicans (Lamiaceae) in the transfer of calcium and formation of calcium oxalate crystals

Com o objetivo de estudar a relação entre cristais de oxalato de cálcio e floema, fragmentos de folhas de Peltodon radicans foram fixados e processados, segundo métodos usuais, para estudos ao microscópio de luz e eletrônico de transmissão. Observou-se que os cristais ocorrem nas células da bainha do feixe, lateralmente em relação ao floema. Células intermediárias estabelecem conexão entre elemento crivado e células da bainha, portadoras de cristais, com crescimento intrusivo entre estas. Íons cálcio são abundantes no citoplasma das células da bainha que contém cristais de oxalato de cálcio. Nas células intermediárias a detecção ultra-citoquímica de cálcio também apresentou resultados positivos, enquanto nos elementos crivados a presença deste íon não foi constatada. Há, portanto, um gradiente crescente de concentração de cálcio dos elementos crivados para as células da bainha. Assim, formulamos a hipótese de que a formação de cristais de oxalato de cálcio tem, em P. radicans, o objetivo de controlar os níveis de cálcio citossólico nos elementos crivados.

Analysis of Ca-PZT powder obtained by the Pechini and partial oxalate methods

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis and characterization of PLZT (9/65/35) by the Pechini method and partial oxalate

ZrTiO4 (ZT), obtained by the Pechini method, was used as precursor for obtaining PLZT (lead lanthanum zirconium titanate). An aqueous solution of oxalic acid was prepared with particles of ZT, Pb(NO3)(2) and La2O3. After the PbC2O4 and La2O3 precipitate on ZT particles, the materials were calcined and X-ray diffraction (XRD) showed the cubic phase of PLZT. This material was sintered, in two steps, and a density of about 8.0 g/cm(3) was obtained. After the second sintering the XRD pattern showed the occurrence of tetragonal and rhombohedral phases. This was caused by a stoichiometric deviation and the material showed a high optical transparency. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Thermal decomposition and rehydration of strontium oxalate: morphological evolution

Undoped and Eu3+ doped monohydrate strontium oxalate samples were precipitated under ultrasound and conventional stirring and were heated at different temperatures. All samples were characterized by X-ray powder diffraction (XDR), infrared spectra (IR) and scanning electron microscopy (SEM). Monohydrate, dehydrate oxalates and carbonate particles are ellipsoids indicating a topotatic process. Particle size decrease is observed when ultrasound stirring and europium. doping are used and rehydration of strontium oxalate results in uniform hexagonal particle shape. An oxide and carbonate mixture is obtained from oxalates treated at 1050 degreesC and its suspension in water undergoes incomplete hydrolysis. The products from this incomplete hydrolysis present dendrite shape particles only when the former is precipitated under ultrasound stirring. In this process, surface energy is important for particle dispersion and ultrasound supplies activation energy to oxalate precursor. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

High sinterability of Ca-PZT, synthesized by polymeric and partial oxalate process

This study includes Ca-PZT in the morphotropic phase boundary, MPB process combining the Pechini method, (ZT) and the Partial oxalate method (Ca-PZT) by obtaining single phase particles of ZT phase with a high specific surface area (similar to 110 m(2)/g at 550 degrees C) and narrow particle size distribution. Lead and calcium oxalates were precipitated onto the ZT particle surface and reacted to a solid state interface ZT/Ca-PZT/PbO-CaO. A deviation of a coexistence region from F-T- and F-R-phases to F-R-phase (Zr rich region) was observed. Strong surface area reduction occurs by Ca-PZT crystallization at about 700 degreesC, and demonstrated high sinterability (2.40 m(2)/g - 350 nm) with apparent densities near to 99.9%. Different processing methods did not demonstrate superior results. Studies of calcined powder shows a high sinterability of powder calcined 3 h at 700 degrees C and sintered 3 h at 1000 degreesC coming up to 99.8% of relative density. (C) 2001 Kluwer Academic Publishers.

Seasonal presence of acicular calcium oxalate crystals in the cambial zone of Citharexylum myrianthum (Verbenaceae)

This study focuses on the seasonal presence of acicular crystals in the cambial zone of Citharexylum myrianthum Chain. (Verbenaceae). Specimens collected in different months from 1996 to 2000 were examined for the abundance of acicular crystals in the cambium. This information was correlated with the phenology of the species and the climate of the region. Acicular calcium oxalate crystals were found in cambial fusiform and ray cell initials, as well as in their daughter cells. An abundance of crystals was observed during periods of water deficit and leaf fall (July). Fewer crystals were found in the beginning of the wet season and bud swelling (September). When trees were flowering and the soil was wet (November and December), acicular crystals were rarely observed. During this period, acicular crystals were found in differentiating phloem and xylem parenchyma cells, in fully differentiated phloem cells, but not in fully differentiated xylem cells.

From tin oxalate to (Fe, Co, Nb)-doped SnO(2): Sintering behavior, microstructural and electrical features

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

Mechanism of phase formation in Pb(ZrxTi1-x)O3 synthesized by a partial oxalate method

The phase formation mechanism, as well as the morphotropic phase boundary, of lead zirconate titanate (PZT) processed by a partial oxalate method was investigated by simultaneous thermal analysis (TG-DTA) and by qualitative and quantitative X-ray diffraction (XRD). The results show that the ZrxTi1-xO2 (ZT) phase reacts with PbO forming the PZT phase without intermediate phases. XRD analysis showed the coexistence of rhombohedral and tetragonal phases for 0.47 ≤ x ≤ 0.55 with the phase boundary composition for x = 0.51. For low calcination temperatures, preferential formation of the PZT rhombohedral phase was observed. A model for phase formation of PZT by the partial oxalate method is proposed based on the existence of two interfaces of reaction (PbO-PZT and PZT-ZT) and diffusion of cations.

Determination of Oxalate in Grass by FIA with a Spectrophotometric Detection System Using a Two Enzyme Reactor

A new methodology for soluble oxalic acid determination in grass samples was developed using a two enzyme reactor in an FIA system. The reactor consisted of 3 U of oxalate oxidase and 100 U of peroxidase immobilized on Sorghum vulgare seeds activated with glutaraldehyde. The carbon dioxide was monitored spectrophotometrically, after reacting with an acid-base indicator (Bromocresol Purple) after it permeated through a PTFE membrane. A linear response range was observed between 0.25 and 1.00mmol l-1 of oxalic acid; the data was fit by the equation A=-0.8(±1.5)+ 57.2(±2.5)[oxalate], with a correlation coefficient of 0.9971 and a relative standard deviation of 2% for n=5. The variance for a 0.25 mmol l-1 oxalic acid standard solution was lower than 4% for 11 measurements. The FIA system allows analysis of 20 samples per hour without prior treatment. The proposed method showed a good correlation with that of the Sigma Kit.

Oxalate determination in urine using an immobilized enzyme on Sorghum vulgare seeds in a flow injection conductimetric system

A flow-injection (FI) method was developed for the determination of oxalate in urine. It was based on the use of oxalate oxidase (E.C. 1.2.3.4) immobilized on ground seeds of the BR-303 Sorghum vulgare variety. A reactor was filled with this activated material, and the samples (200 μL) containing oxalate were passed through it, carried by a deionized water flow. The carbon dioxide produced by the enzyme reaction permeated through a microporous PTFE membrane, and was received in a water acceptor stream, promoting conductivity changes proportional to the oxalate concentration in the sample. The results obtained showed a useful linear range from 0.05 to 0.50 mmol dm-3. The proposed method, when compared with the Sigma enzymatic procedure, showed good correlation (Y = 0.006(±0.016) + 0.98(±0.019)X; r = 0.9995, Y = conductivity in μS, and X = concentration in mmol dm-3), selectivity, and sensitivity. The new immobilization approach promotes greater stability, allowing oxalate determination for 6 months. About 13 determinations can be performed per hour. The precision of the proposed method is about ± 3.2 % (r.s.d).