Thermal studies on solid compounds of 4-chlorobenzylidenepyruvate of some alkali earth metals

Solid-state M-4-Cl-BP compounds, where M stands for bivalent Mg, Ca, Sr, Ba and 4-Cl-BP is 4-chlorobenzylidenepyruvate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, elemental analysis and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to informations about the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes.

Effect of substitution of [Pd(PPh3)(4)] by related compounds as catalysts in reactions of organic syntheses

The effect of substitution of [Pd(PPh3)(4)], which is unstable in air, by complexes of the type [MCl2L2] (M = Pd, Pt; L = AsPh3, SbPh3), [PdL4](L = PPh3, AsPh3, SbPh3) and [NiX2(PPh3)(2)] on the syntheses of thioethers, acetylenes and ketones is described.

Dynamics of aggregate stability influenced by soil management and crop residues

The type of tillage and crop systems used can either degrade or cause a recovery of the structure of agricultural soils. The objective of this study was to determine the structural stability of the soil using mean weight diameter (MWD) of soil aggregates in three different periods of a succession of crops consisting of beans/cover plants/maize under no tillage (NT) and conventional tillage (CT) management systems. Soils were sampled at 0- to 5-cm and 5- to 15-cm depths in three periods (P1, P2, P3): 1) November 2002 (spring/summer), 2) April 2003 (beginning of autumn), and 3) December 2003 (end of spring/beginning of summer). Aggregate stability was determined by wet sieving. The effects of the tillage systems, vegetal residues, and sampling depths on the structural stability of the aggregates were assessed and then related to organic matter (OM) contents. Aggregate stability showed temporal variation as a function of OM contents and sampling period. No tillage led to high MWD values in all study periods. The lowest MWD values and OM contents were observed 4 months after the management of the residues of cover plants. This finding is consistent with the fact that at the time of the samplings, most of the OM had already mineralized. The residues of sunn-hemp, millet, and spontaneous vegetation showed similar effects on soil aggregate stability.

Thermal analysis and electrochemical study of Hg reactions on Pt-30% Ir alloy electrode

Thermogravimetry (TG), cyclic voltammetry (CV) and other analytical techniques were used to study the reactions of mercury with Pt-30% Ir alloy. The results allowed to suggest that an electrodeposited mercury film interacts with the substrate and when subjected to heat or electrochemical removal at least four mass loss steps or five peaks appeared during the mercury desorption process. The first two steps were attributed to Hg(0) removal probably from the bulk and from the adsorbed monolayer which wets the electrode surface. These two processes are responsible for peaks D and F in the cyclic voltammograms. The last two peaks (G, H) in CV were ascribed to the intermetallic compound decomposition. In TG curves, the last two steps were attributed to the PtHg4 (third step), and PtHg2 decomposition followed by Hg removal from the subsurface. The PtHg2 was formed by an eutectoide reaction: PtHg -> PtHg2+Hg(Pt-Ir). The Hg diffused to the subsurface was not detectable by cyclic voltammetry.

THE EFFECT OF POSITRONIUM FORMATION IN POSITRON ALKALI-ATOM SCATTERING

We study e+-Na, e+-K, and e+-Rb scattering using the close coupling approach in the static and coupled static expansion schemes. We calculate partial wave elastic scattering phase shifts and total elastic and Ps formation cross sections up to an incident positron energy of 100 eV. The effect of the positronium formation channel on the elastic channel is found to be strong in all cases up to an incident positron energy of 10 eV. We also make an estimate of the total cross section which exhibits a minimum as a function of energy at low energies.

Raman scattering, differential scanning calorimetry and Nd3+ spectroscopy in alkali niobium tellurite glasses

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2-Nb2O5-(0.5K(2)O-0.5Li(2)O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the alpha-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd-Ofelt Omega(lambda) intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Solid-state chelates of ethylenediamine-tetraacetate with alkali earth metals

Solid-state M-EDTA chelates, where M represents the divalent ions Mg(II), Ca(II), Sr(II) or Ba(II) and EDTA is ethylenediaminetetraacetate anion, were synthesized. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC) and X-ray diffraction powder patterns have been used to characterize and to study the thermal behaviour of these chelates. The results provided information concerning the stoichiometry, crystallinity, thermal stability and thermal decomposition.

Simple and fast spectrophotometric determination of H2O2 in photo-Fenton reactions using metavanadate

This work proposes a spectrophotometric method for the determination of hydrogen peroxide during photodegradation reactions. The method is based on the reaction of H2O2 with amonium metavanadate in acidic medium, which results in the formation of a red-orange color peroxovanadium cation, with maximum absorbance at 450 nm. The method was optimized using the multivariate analysis providing the minimum concentration of vanadate (6.2 mmol L-1) for the maximum absorbance signal. Under these conditions, the detection limit is 143 mu mol L-1. The reaction product showed to be very stable for samples of peroxide concentrations up to 3 mmol L-1 at room temperature during 180 h. For higher concentrations however, samples must be kept refrigerated (4 degrees C) or diluted. The method showed no interference of Cl- (0.2-1.3 mmol L-1), NO3- (0.3-1.0 mmol L-1), Fe3+, (0.2-1.2 mmol L-1) and 2,4-dichlorophenol (DCP) (0.2-1.0 mmol L-1). When compared to iodometric titration, the vanadate method showed a good agreament. The method was applied for the evaluation of peroxide consumption during photo-Fenton degradation of 2,4-dichlorophenol using blacklight irradiation. (c) 2004 Elsevier B.V. All rights reserved.

LATTICE-DYNAMICS OF ALKALI-METALS IN A 3-BODY INTERACTION

The original model of Das et al. is modified in extending the electron-ion interaction on a three-body forces and including the crystal equilibrium condition to reduce one independent parameter. We studied the phonon dispersion relations along the three principal symmetry directions i.e. [xi, 0, 0], [xi, xi, 0] and [xi, xi, xi] and theta-T curves of alkali metals, Na, K, Rb, Cs and Li. There is close agreement between the computed results and the experimental observations.

Mineral trioxide aggregate as a root canal filling material in reimplanted teeth. Microscopic analysis in monkeys

This study analyzed mineral trioxide aggregate (MTA) as a root canal filling material for the immediate reimplantation of monkey teeth. Four adult capuchin monkeys Cebus apella were used, which had their maxillary and mandibular lateral incisors on both sides extracted and reimplanted after 15 min. During the extra-alveolar period, the teeth were kept in saline solution and after reimplantation retention was performed with a stainless steel wire and composite resin for 14 days. After 7 days, the reimplanted teeth were submitted to endodontic treatment with biomechanics up to file n. 30 and irrigation with a saturated solution of calcium hydroxide [Ca(OH)(2)], and then divided into two study groups: group I - root canal filled with a Ca(OH)(2) paste, and group II - root canal filled with MTA. Radiographic follow up was performed at 30, 60 and 90 days postoperatively, and after 180 days the animals were killed and specimens were processed for histomorphological analysis. The results revealed that most specimens of both groups presented organized periodontal ligament with no inflammation. The resorptions observed were surface resorptions and were repaired by cementum. Both MTA and Ca(OH)(2) were good root canal filling materials for immediately reimplanted teeth, providing good repair and also allowing biological sealing of some lateral canals. There was no significant difference between the study groups (alpha = 29.60%).

Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion

The low-weight Pd(II) coordination polymers [(N(3))(HL)Pd {Pd(3)(mu-N(3))(mu-L)(5)}10(mu-L)(2)Pd(L)(HL)]{L = Pz(-) (1); mPz(-) (2), IPz(-)(3)} and [(N(3))(HPz)Pd{Pd(6)(mu-N(3))(2)(mu-PZ)(5)(mu-L)(5)}(10)(mu-L)(2)Pd(Pz)(HPz)] {L = mPz(-) (4), dmPz(-) (5); IPz(-) (6)} {L = pyrazolate (Pz(-)), 4-methylpyrazolate(mPz(-)), 4-iodopyrazo late (IPz(-)), 3,5-dimethylpyrazolate (dmPz(-))} have been prepared in this work. IR spectra clearly indicated the exobidentate nature of pyrazolato ligands as well the end-on coordination mode of the azido group. The molecular weight determinations by osmometry indicated that the species have a low degree of polymerization (n = 10). NMR experiments showed two pyrazolate environments in a 2:1 ratio, being assigned to the six-membered ring Pd(mu-L)(2)Pd and the Pd(mu-N(3))(mu-L)Pd metallocycle, respectively. UV-visible spectroscopy gave further evidences for the oligomeric structures of 1-6. Some alternative structures for the isostructural polymers have been suggested. (c) 2005 Elsevier Ltd. All rights reserved.

Exploiting Cascade Reactions in Bienzyme Layer-by-Layer Films

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