Thermal behaviour study of solid state compounds of manganese (II), zinc (II) and lead (II) with cinnamic acid

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

Thermoanalytical study of the complexes of 4-dimetilaminocinnamylidenepiruvate with manganese (II), cobalt (II), nickel (II), cupper (II), zinc (II) and lead (II), in the solid state

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

A thermal analysis study of dithizone and dithizonates of mercury, silver and bismuth

Foram preparados os ditizonatos de Hg (I), Ag (I) e Bi (III). Termogravimetria (TG), termogravimetria derivada (DTG), calorimetria exploratória diferencial (DSC), difratometria de raios X pelo método do pó e análise elementar foram usados para caracterizar e para estudar a estabilidade térmica e a decomposição térmica da ditizona e destes ditizonatos.

Thermal decomposition and stability in a series of heterobimetallic carbonyl compounds of the type [Fe(CO)4(HgX)2] (X=Cl, Br, I)

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

Effect of aging on the stability of ceramic foams prepared by thermostimulated sol-gel process

This work presents a new route of preparation of zirconium ceramic foams based on the thermostimulated sol-gel process. This method produces gelled bodies with up to 90% of porosity in the wet gel and can be used to make complex-shaped components. Unfortunately, the shrinkage during the drying step allows to a catastrophic reduction (50%) of the foam porosity. To improve the foam stability we carried out a systematic study of the effect of gel foam aging on the drying process. Samples were aged in closed vessel at 25 C during different time period (from 6 to 240 h). The shrinkage and the mass loss during drying at 50 C were measured in situ, using a non-contact technique performed with a special apparatus. The results show that the total linear shrinkage decreases from 46% to 8% as the aging period increase from 6 to 240 h. This behavior is followed by a small change of total mass loss, from 42 to 54%. It indicates that by aging the structural stiffness of the foams increases due to secondary condensation reactions. Thus, by controlling the aging period, the porosity can be increased from 67 to 75% and the average size of mesopores of dried foams can be screened from 0.3 to 0.9 mum. Finally, these results demonstrate that the thermostimulated sol-gel transition provides a potential route to ceramic foams manufacture.

Study of alternative schemes for the parameterization step of the continuation power flow method based on physical parameters, part I: Mathematical modeling

The conventional power flow method is considered to be inadequate to obtain the maximum loading point because of the singularity of Jacobian matrix. Continuation methods are efficient tools for solving this kind of problem since different parameterization schemes can be used to avoid such ill-conditioning problems. This paper presents the details of new schemes for the parameterization step of the continuation power flow method. The new parameterization options are based on physical parameters, namely, the total power losses (real and reactive), the power at the slack bus (real or reactive), the reactive power at generation buses, and transmission line power losses (real and reactive). The simulation results obtained with the new approach for the IEEE test systems (14, 30, 57, and 118 buses) are presented and discussed in the companion paper. The results show that the characteristics of the conventional method are not only preserved but also improved.

Study of alternative schemes for the parameterization step of the continuation power flow method based on physical parameters, part II: Performance evaluation

New parameterization schemes have been proposed by the authors in Part I of this paper. In this part these new options for the parameterization of power flow equations are tested, namely, the total power losses (real and reactive), the power at the slack bus (real or reactive), the reactive power at generation buses, and the transmission line power losses (real and reactive). These different parameterization schemes can be used to obtain the maximum loading point without ill-conditioning problems, once the singularity of Jacobian matrix is avoided. The results obtained with the new approach for the IEEE test systems (14, 30, 57, and 118 buses) show that the characteristics of the conventional method are not only preserved but also improved. In addition, it is shown that the proposed method and the conventional one can be switched during the tracing of PV curves to determine, with few iterations, all points of the PV curve. Several tests were also carried out to compare the performance of the proposed parameterization schemes for the continuation power flow method with the use of both the secant and tangent predictors.

Long-term histopathologic evaluation of inferior vena cava after modified Greenfield filter implantation - Experimental study in sheep

Aim. The authors assess a modified Greenfield filter (GF) for the long-term patency, filter tilting and histopathologic alterations of the inferior vena cava (IVC).Methods. Adult sheep (n=7) underwent modified GF placement in the IVC. Cavograms were obtained every 3 months and pulmonary angiography at 12 months. Histopathologic and scanning electron microscopy (SEM) analyses were performed on the IVC explanted at 12 months.Results. Cavograms showed that all IVC were patent at the end of the study. Filter tilting occurred in 2/7 animals and extrusion of struts was not observed. Macroscopic examination at explantation showed minimal venous wall thickening. Microscopic examination showed minimal IVC fibrosis and intimal hyperplasia. SEM showed endothelium on the IVC surface at the filter implantation site and a presumed endothelial layer covering partially or totally the struts. The interface filter-IVC was covered by deposits of leucocytes and platelets. No signs of pulmonary embolism were found in all pulmonary angiograms of both groups.Conclusion. The modified filter presented good biocompatibility, stability and absence of thrombogenicity at 12 months. It presented low tendency to tilting and extrusion of struts. The long-term histopathologic alterations in vena caval wall were minimal and the appearance of the studied filters in the IVC was similar to stents placed in the arterial system.

Thermal study of cyclopalladated complexes of the type [Pd-2(dmba)(2)X-2(bpe)] - (X=NO3-, Cl-, N-3(-), NCO-, NCS-; bpe=trans-1,2-bis(4-pyridyl)ethylene)

The synthesis, characterization and thermal analysis of the novel cyclometallated compounds [Pd-2(dmba)(2)Cl-2(mu-bpe)] (1), [Pd-2(dmba)(2)(N-3)(2)(mu-bpe)] (2), [Pd-2(dmba)(2)(NCO)(2)(mu-bpe)] (3), [Pd-2(dmba)(2)(SCN)(2)(mu-bpe)] (4), [Pd-2(dmba)(2)(NO3)(2)(mu-bpe)] (5) (bpe=trans-1,2-bis(4-pyridyl)ethylene; dmba=N,N-dimethylbenzylamine) are described. The thermal stability of [Pd-2(dmba)(2)X-2(mu-bpe)] complexes varies in the sequence 1 > 4 > 3 > 2 > 5. The final residues of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.

Whydration effects on DNA double helix stability modulates ligand binding to natural DNA in response to changes in water activity

In this work we present evidence that water molecules are actively involved on the control of binding affinity and binding site discrimination of a drug to natural DNA. In a previous study, the effect of water activity (a(w)) on the energetic parameters of actinomycin-D intercalation to natural DNA was determined using the osmotic stress method (39). This earlier study has shown evidence that water molecules act as an allosteric regulator of ligand binding to DNA via the effect of water activity on the long-range stability of the DNA secondary structure. In this work we have carried out DNA circularization experiments using the plasmid pUC18 in the absence of drugs and in the presence of different neutral solutes to evaluate the contribution of water activity to the energetics of DNA helix unwinding. The contribution of water to these independent reactions were made explicit by the description of how the changes in the free energy of ligand binding to DNA and in the free energy associated with DNA helix torsional deformation are linked to a(w) via changes in structural hydration. Taken together, the results of these studies reveal an extensive linkage between ligand binding affinity and site binding discrimination, and long range helix conformational changes and DNA hydration, This is strong evidence that water molecules work as a classical allosteric regulator of ligand binding to the DNA via its contribution to the stability of the double helix secondary structure, suggesting a possible mechanism by which the biochemical machinery of DNA processing takes advantage of the low activity of water into the cellular milieu.

Experimental and theoretical study on the piezoelectric behavior of barium doped PZT

An experimental and theoretical study of the ferroelectric and piezoelectric behavior of PZT doped with barium is presented. Ab initio perturbed ion calculations was carried out. The properties, such as remnant polarization, coercive field and the coupling factor of the PZT at constant sintering temperature was compared with the Zr4+/Ti4+ ions dislocation energy and the lattice interaction energy. An agreement between the experimental and theoretical results, with a decrease of the interaction energy and an inversion of the energy stability from tetragonal to rhombohedral phase was observed. (C) 1999 Kluwer Academic Publishers.

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.

Cation-oxygen interaction and oxygen stability in CaCu3Ti4O12 and CdCu3Ti4O12 lattices

The cubic perovskite related material CaCu3Ti4O12 has attracted a great deal of attention due to the high values of the static dielectric constant, of order 104, approximately constant in the temperature range 100-600 K. The substitution of Ca by Cd results in a similar temperature dependence but a static dielectric constant more than one order of magnitude lower. A theoretical electronic structure study is performed on CaCu3Ti4O12 (CCTO) and CdCu3Ti4O12 (CdCTO) using a tight binding with overlap method. Although the calculations are performed in a paramagnetic configuration, excellent agreement with experiment was found for the calculated band gap of CCTO. In spite of the fact that the band structures of both systems look practically the same, a significant difference is found in the calculated bond strength of Ca-O and Cd-O pairs, driven by the presence of Ti, with Ca-O interaction in CCTO loosened with respect to Cd-O interaction in the cadmium compound. It is suggested that O vacancies are more easily formed in CCTO, this being related to the lower electronegativity of Ca as compared to Cd. The formation of oxygen vacancies could be the origin of the difference in the static dielectric constant of the two compounds.

Postsurgical stability of oropharyngeal airway changes following counter-clockwise maxillo-mandibular advancement surgery

Purpose: This study evaluated oropharyngeal airway changes and stability following surgical counter-clockwise rotation and advancement of the maxillo-mandibular complex.Methods and Patients: Fifty-six adults (48 females, 8 males), between 15 and 51 years of age, were treated with Le Fort I osteotomies and bilateral mandibular ramus sagittal split osteotomies to advance the maxillo-mandibular complex with a counter-clockwise rotation. The average postsurgical follow-up was 34 months. Each patient's lateral cephalograms were traced, digitized twice, and averaged to estimate Surgical changes (T2-T1) and Postsurgical changes (T3-T2).Results: During surgery, the occlusal plane angle decreased significantly (8.6 +/- 5.8 degrees) and the maxillo-mandibular complex advanced and rotated counter-clock-wise. The maxilla moved forward (2.4 +/- 2.7 mm) at ANS and the mandible was advanced 13.1 +/- 5.1 min at menton, 10 +/- 4.4 mm at point B, and 6.9 +/- 3.7 mm at lower incisor edge. Postsurgical hard tissue changes were not statistically significant. While the upper oropharyngeal airway decreased significantly (4.2 +/- 3.4 min) immediately after surgery, the narrowest retropalatal, lowest retropalatal airway, and the narrowest retroglossal airway measurements increased 2.9 +/- 2.7, 3.7 +/- 3.2, and 4.4 +/- 4.4 mm, respectively. Over the average 34 months Postsurgical period, upper retropalatal airway increased 3.9 +/- 3.7 mm, while narrowest retropalatal, lowest retropalatal airway, and narrowest retroglossal airway remained stable. Head posture showed flexure immediately after Surgery (4.8 +/- 5.9 degrees) and extension postsurgically (1.6 +/- 5.6 degrees).Conclusion: Maxillo-mandibular advancement with counter-clockwise rotation produces immediate increases in middle and lower oropharyngeal airway dimensions, which were constrained by changes in head posture but remain stable over the postsurgical period. The upper oropharyngeal airway space increased only on the longest follow-up. (C) 2006 American Association of Oral and Maxillofacial Surgeons.

A Bayesian approach for assessing the stability of genotypes

Several statistical models can be used for assessing genotype X environment interaction (GEI) and studying genotypic stability. The objectives of this research were to show how (i) to use Bayesian methodology for computing Shukla's phenotypic stability variance and (ii) to incorporate prior information on the parameters for better estimation. Potato [Solanum tuberosum subsp. andigenum (Juz. & Bukasov) Hawkes], wheat (Triticum aestivum L.), and maize (Zea mays L.) multi environment trials (MET) were used for illustrating the application of the Bayes paradigm. The potato trial included 15 genotypes, but prior information for just three genotypes was used. The wheat trial used prior information on all 10 genotypes included in the trial, whereas for the maize trial, noninformative priors for the nine genotypes was used. Concerning the posterior distribution of the genotypic means, the maize MET with 20 sites gave less disperse posterior distributions of the genotypic means than did the posterior distribution of the genotypic means of the other METs, which included fewer environments. The Bayesian approach allows use of other statistical strategies such as the normal truncated distribution (used in this study). When analyzing grain yield, a lower bound of zero and an upper bound set by the researcher's experience can be used. The Bayesian paradigm offers plant breeders the possibility of computing the probability of a genotype being the best performer. The results of this study show that although some genotypes may have a very low probability of being the best in all sites, they have a relatively good chance of being among the five highest yielding genotypes.