Thermal study of CoxZn7-xSb2O12 spinel obtained by pechini method using different alcohols

With the aim of obtaining materials with applications in pigments, Co_xZn_7-xSb₂O₁₂ spinels were synthesized using the Pechini method. This method consists in the formation of a polymeric net, where the metallic cations are homogeneously distributed. In this work, two types of alcohol (ethyl glycol and ethylene glycol) were used for the synthesis of a zinc antimoniate spinel, Co_xZn_7-xSb₂O₁₂ (x=0-7). The materials were characterized by termogravimetry (TG) and differential thermal analysis (DTA). TG results indicated a decrease in total mass loss when cobalt was added to the solution substituting zinc, for samples prepared using the two different alcohols. Decomposition temperatures, obtained by TG and DTA, presented a decreasing behavior as cobalt was added to the material. In relation to the alcohols, all results indicated a better polymerization of the resin when ethylene glycol was used, being the most indicated one for cation immobilization. X-ray diffraction did not show differences between the two alcohols - both presented the spinel phase (Co, Zn)_2.33Sb₀.₆₇O₄. Samples with higher quantity of cobalt also presented ilmenite phase (Co, Zn)Sb₂O₆. This revised version was published online in August 2006 with corrections to the Cover Date.     

Simulation of aerated lagoon using artificial neural networks and multivariate regression techniques

The aim of this study was to develop an empirical model that provides accurate predictions of the biochemical oxygen demand of the output stream from the aerated lagoon at International Paper of Brazil, one of the major pulp and paper plants in Brazil. Predictive models were calculated from functional link neural networks (FLNNs), multiple linear regression, principal components regression, and partial least-squares regression (PLSR). Improvement in FLNN modeling capability was observed when the data were preprocessed using the PLSR technique. PLSR also proved to be a powerful linear regression technique for this problem, which presents operational data limitations.     

Particle shape in thixotropic aluminium and thorium molybdates gels

Summary Electron microscope examination of thixotropic aluminium and thorium molybdate gels shows that one hour after formation they are constituted by short fibrils of small axial ratio. The fibrils of the aluminium molybdate gels, with ageing at room temperature or with boiling, increase in diameter and length; the fibrous shape of the particles is maintained after two and a half years of ageing; all fibrils are crystalline by electron diffraction. The fibrils of the thorium molybdate gels, except in the gels containing hydrochloric acid, change with ageing at room temperature or with boiling, into plates of hexagonal, elliptical or rectangular profile; the fibrils and plates are crystalline and have the same electron diffraction pattern as the fibrils.This work was aided, in part, by grants from Conselho Nacional de Pesquisas and the Rockefeller Foundation.     

Potentiometric studies on the complexation of copper(II) by phenolic acids as discrete ligand models of humic substances

Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pK_a1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pK_a2 and pK_a3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group.     

Phase separation of p53 precedes aggregation and is affected by oncogenic mutations and ligands

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF). The mechanism of the formation of the aggregates in the nucleus remains uncertain. The present study demonstrated that the DNA-binding domain of p53 (p53C) underwent phase separation (PS) on the pathway to aggregation under various conditions. p53C phase separated in the presence of the crowding agent polyethylene glycol (PEG). Similarly, mutant p53C (M237I and R249S) underwent PS; however, the process evolved to a solid-like phase transition faster than that in the case of wild-type p53C. The data obtained by microscopy of live cells indicated that transfection of mutant full-length p53 into the cells tended to result in PS and phase transition (PT) in the nuclear compartments, which are likely the cause of the GoF effects. Fluorescence recovery after photobleaching (FRAP) experiments revealed liquid characteristics of the condensates in the nucleus. Mutant p53 tended to undergo gel- and solid-like phase transitions in the nucleus and in nuclear bodies demonstrated by slow and incomplete recovery of fluorescence after photobleaching. Polyanions, such as heparin and RNA, were able to modulate PS and PT in vitro. Heparin apparently stabilized the condensates in a gel-like state, and RNA apparently induced a solid-like state of the protein even in the absence of PEG. Conditions that destabilize p53C into a molten globule conformation also produced liquid droplets in the absence of crowding. The disordered transactivation domain (TAD) modulated both phase separation and amyloid aggregation. In summary, our data provide mechanistic insight into the formation of p53 condensates and conditions that may result in the formation of aggregated structures, such as mutant amyloid oligomers, in cancer. The pathway of mutant p53 from liquid droplets to gel-like and solid-like (amyloid) species may be a suitable target for anticancer therapy.

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF).     

Synthesis of non-agglomerated Ba<Subscript>0.77</Subscript>Ca<Subscript>0.23</Subscript>TiO<Subscript>3</Subscript> nanopowders by a modified polymeric precursor method

In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba_0.77Ca_0.23TiO₃ nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis, morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy. In summary, Ba_0.77Ca_0.23TiO₃ nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution (30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the chelation in higher pHs.     

Capillary zone electrophoresis of cationic and anionic drugs in methanol

The actual mobilities and dissociation constants of acidic and basic pharmaceuticals were determined in methanol. Actual mobilities were derived from the dependence of the effective mobilities of the analytes on the pH of the methanolic background electrolyte solution (pH(MeOH)). The pKa values of the pharmaceuticals in methanol (pK(a,MeOH)) were calculated by non-linear curve fitting to the measured mobility values. It was found that the shift in pKa value (when compounds were transferred from water to methanol) increased with the acidity of the analyte. The average pKa shift for compounds exhibiting acidic properties in water was ca. 5.5 units, and the shift for basic compounds about 2 units. As was shown for a mixture of beta-blockers, the calculated actual mobilities and pKa values can be utilised in the optimisation of pH conditions for separation. The practical value of the method was illustrated by the analysis of urine samples.     

Trace elemental determination in alcohol automotive fuel by electrothermal atomic absorption spectrometry

Suitable analytical methodologies were developed allowing direct determination of As, Cu, Fe, Pb, Sb and Sn in alcohol fuel samples by electrothermal atomic absorption spectrometry. Different chemical modification approaches were tested and compared in terms of analytical performance and in practical terms. Experimental conditions were optimized allowing little sample dilution and use of calibration curves prepared with aqueous inorganic analyte standards. Methodologies were tested with analyte spiked alcohol samples. Good analyte recoveries from spiked alcohol samples, precision better than 10% and limits of detection in the sub μg l⁻¹ range were achieved.