Mono and dinuclear Pd(II) complexes with pyrazole and imidazole-type ligands

The cyanate-bridged cyclopalladated compound [Pd(C(2),N-dmba)(mu-NCO)](2) (dmba=N,N-dimethylbenzylamine) reacts in acetone with pyrazole (pz), 3,5-dimethylpyrazole (dmpz), imidazole (imz) and 2-methylimidazole (mimz) to give [Pd(2)(C(2),N-dmba)(2)(mu-NCO)(mu-pz)] (1), [Pd(2)(C(2),N-dmba)(2)(mu-NCO)(mu-dmpz)] (2), [Pd(C(2),N-dmba)(NCO)(imz)] (3) and [Pd(C(2),N-dmba)(NCO)(mimz)] (4), respectively. The compounds were characterized by elemental analysis, IR spectroscopy and TG. The thermal decomposition of the compounds occurs in three consecutive steps and the final decomposition products were identified as Pd(0) by X-ray powder diffraction. The thermal stability order of the complexes is 2 > 3 > 1 > 4.

Monitoring the process mean and variance using a synthetic control chart with two-stage testing

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nanocomposites of Styrene-Butadiene Rubber and Synthetic Anatase Obtained by a Colloidal Route and Their Photooxidation

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

Size, electrophoretic mobility, and ion dissociation of vesicles prepared with synthetic amphiphiles

Vesicles prepared with synthetic amphiphiles (dioctadecyldimethylammonium bromide and chloride, dihexadecyl phosphate and its sodium salt) were obtained by sonication, ethanol injections, and chloroform injections. The hydrodynamic diameter of vesicles (Dh), estimated from the diffusivity measured by quasielastic light scattering, ranged from 230 to 3000 Å. The electrophoretic mobility (Um) was measured by free-flow electrophoresis. The zeta potential (ζ) and the degree of counterion dissociation (α) of the vesicles were calculated from Um and conductivity data, α decreased with increasing Dh of the vesicles, probably due to the decreasing headgroup area and the increasing counterion association needed to relax the surface electrostatic potential. The electrophoretic mobility was also calculated (Uc) according to an impenetrable, nonconducting sphere model with a spherically symmetric charge distribution approximation. Within the limits of the experimental error(s) of the (different) methods employed and the assumptions made in the calculations, the fact that the Um/Uc ratio ranged from 1.3 to 7.5 was considered to be a good agreement between the calculated and the experimental values. © 1990 American Chemical Society.

Effect of organic synthetic food colours on mitochondrial respiration

Eleven organic synthetic dyes, currently or formerly used as food colours in Brazil, were tested to determine their effect on mitochondrial respiration in mitochondria isolated from rat liver and kidney. The compounds tested were: Erythrosine, Ponceau 4R, Allura Red, Sunset yellow, Tartrazine, Amaranth, Brilliant Blue, Indigotine Blue, Fast Red E, Orange GGN and Scarlet GN. All food colours tested inhibited mitochondrial respiration (State III respiration, uncoupled) supported either by α-ketoglutarate or succinate. this inhibition varied largely, e.g. from 100% to 16% for Erythrosine and Tartrazine respectively, at a concentration of 0.1 mg food colour per mitochondrial protein. Both rat liver and kidney mitochondria showed similar patterns of inhibition among the food colours tested. This effect was dose related and the concentration to give 50% inhibition was determined for some of the dyes. The xanthene dye Erythrosine, which showed the strongest effect, was selected for further investigation on mitochondria in vivo.

Phase behavior of synthetic amphiphile vesicles investigated by calorimetry and fluorescence methods

The understanding of biological membranes may be improved by investigating physical properties of vesicles from natural or synthetic amphiphiles. The application of vesicles as mimetic agents depends on the knowledgment of their structure and properties. Vesicles having different curvature and size may be obtained using different preparation protocols. We have used differential scanning calorimetry (DSC) and steady-state fluorescence to investigate the gel to liquid-crystal phase transition of vesicles prepared by sonication (SUV) and non-sonication (GUV) of the synthetic dioctadecyldimethylammonium bromide (DODAB) in aqueous solution. DSC thermograms for a non-sonicated dispersion show a well-defined pre- and main transition corresponding to two narrow peaks at 36 and 45°C in the first upscan, while in a second upscan, only the main peak was observed. The sharpness of the peaks indicate a cooperative phase behavior for GUV. For a sonicated DODAB dispersion, the first upscan shows a third peak at 40.3°C, whereas for the second upscan the peaks are not well-defined, indicating a less cooperative phase behavior. Alternatively, the fluorescence quantum yield (Φ f) and the anisotropy (r) of trans, trans, trans-1-[4-(3-carboxypropyl)-phenyl]-6-[4-butylphenyl]-1,3,5-hexatriene (4H4A) and the ratio I 1/I 3 of the first to the third vibronic peaks of the pyrene emission spectrum as function of temperature are used as well to describe the phase behavior of DODAB sonicated and non-sonicated dispersions. It is in good agreement with the DSC results that the cooperativity of the thermotropic process is diminished under sonication of the DODAB dispersion, meaning that sonication changes from homogeneous to heterogeneous populations of the amphiphile aggregates. The pre- and main transitions obtained from these techniques are in fairly good accord with results from the literature.

Lead- and copper-complexing extracellular ligands released by Kirchneriella aperta (Chloroccocales, Chlorophyta)

The freshwater planktonic alga Kirchneriella aperta was grown in batch cultures to stationary growth phase. Copper and lead complexation properties of the exudate from stationary and exponential growth phases were determined by titrations monitored by ion-selective electrodes. Molecular weight fractionation dialysis) and analysis of the titration data (Scatchard Plot) revealed that K. aperta releases metal-complexing ligands. Copper is associated with low and high molecular weight compounds, whereas lead forms complexes with only high molecular weight compounds. Gas-liquid chromatography showed that mannose and rhamnose make up 74% of the total high molecular weight organic material, with uronic acids present at 19%.

Renal effects of angiotensin II receptor subtype 1 and 2-selective ligands injected into the paraventricular nucleus of conscious rats

We determined the effects of losartan and CGP42112A (selective ligands of the AT1 and AT2 angiotensin receptors, respectively) and salarasin (a relatively nonselective angiotensin receptor antagonist) on urinary volume and urinary sodium and potassium excretion induced by administration of angiotensin II (ANG II) into the paraventricular nucleus (PVN) of conscious rats. Both the AT1 and AT2 ligands and salarasin administered in the presence of ANG II elicited a concentration-dependent inhibition of urine excretion, but losartan inhibited only 75% of this response. The IC50 for salarasin, CGP42112A, and losartan was 0.01, 0.05, and 6 nM, respectively. Previous treatment with saralasin, CGP42112A and losartan competitively antagonized the natriuretic responses to PVN administration of ANG II, and the IC50 values were 0.09, 0.48, and 10 nM, respectively. The maximum response to losartan was 65% of that obtained with saralasin. Pretreatment with saralasin, losartan, and CGP42112A injected into the PVN caused shifts to the right of the concentration-response curves, but the losartan concentrations were disproportionately greater compared with salarasin or CGP42112A. The IC50 values were 0.06, 0.5, and 7.0 for salarasin, CGP42112A, and losartan, respectively. These results suggest that both AT1 and AT2 receptor subtypes in the PVN are involved in ANG II-related urine, sodium, and potassium excretion, and that the inhibitory responses to AT2 blockade are predominant. Copyright (C) 1999 Elsevier Science B.V.

Toxicity of synthetic piperonyl compounds to leaf-cutting ants and their symbiotic fungus

The development of Leucoagaricus gongylophorus, the fungus cultured by the leaf-cutting ant Atta sexdens was inhibited in vitro by synthetic compounds containing the piperonyl group. In addition, worker ants that were fed daily on an artificial diet to which these compounds were added had a higher mortality rate than the controls. The inhibition of the fungal growth increased with the size of the carbon side chain ranging from C1 through C8 and decreasing thereafter. 1-(3,4-Methylenedioxybenzyloxy)octane (compound 5) was the most active compound and inhibited the fungal development by 80% at a concentration of 15 μg m1-1. With worker ants the toxic effects started with compound 5 and increased with the number of carbons in the side chain. Thus, for the same concentration (100 μg m1-1) the mortality rates observed after 8 days of diet ingestion were 82%, 66% and 42%, for 1-(3,4-methylenedioxybenzyloxy)decane, 1-(3,4-methylenedioxybenzyloxy)dodecane and compound 5, respectively, whereas with commercial piperonyl butoxide the mortality was 68%. The latter compound, which is known as a synergist insecticide, was as inhibitory to the symbiotic fungus as the synthetic compound 5. The possibility of controlling these insects in the future using compounds that can target simultaneously both organisms is discussed. © 2001 Society of Chemical Industry.

Targeting Plasmodium ligands on mosquito salivary glands and midgut with a phage display peptide library

Despite vast efforts and expenditures in the past few decades, malaria continues to kill millions of persons every year, and new approaches for disease control are urgently needed. To complete its life cycle in the mosquito, Plasmodium, the causative agent of malaria, has to traverse the epithelia of the midgut and salivary glands. Although strong circumstantial evidence indicates that parasite interactions with the two organs are specific, hardly any information is available about the interacting molecules. By use of a phage display library, we identified a 12-aa peptide-salivary gland and midgut peptide 1 (SM1)-that binds to the distal lobes of the salivary gland and to the luminal side of the midgut epithelium, but not to the midgut surface facing the hemolymph or to ovaries. The coincidence of the tissues with which parasites and the SM1 peptide interact suggested that the parasite and peptide recognize the same surface ligand. In support of this hypothesis, the SM1 peptide strongly inhibited Plasmodium invasion of salivary gland and midgut epithelia. These experiments suggest a new strategy for the genetic manipulation of mosquito vectorial capacity.

In vitro cytotoxicity of some natural and semi-synthetic isocoumarins from Paepalanthus bromelioides

Numerous natural compounds have a potential for therapeutic applications, but may have to be chemically modified to alter toxic side effects. We investigated structural parameters that could affect the cytotoxicity of isocoumarins similar to 9,10-dihydroxy-5,7-dimethoxy-1H-naphtho(2,3c)pyran-1-one (paepalantine 1). Paepalantine 1 has antimicrobial activity, as well as significant in vitro cytotoxic effects in the McCoy cell line. Two other natural and two semi-synthetic isocoumarins with similar structures obtained from the capitula of Paepalanthus bromelioides were tested on the same cell line by the neutral red assay. Substitution of the 9 and/or 10-OH group made these compounds less cytotoxic.

Crystallographic and spectroscopic studies on palladium(II) complexes containing pyrazole and thiocyanate ligands

Mononuclear palladium(II) complexes containing both pyrazole-type ligands and thiocyanate, of general formula [Pd(SCN) 2(L) 2] {L = pyrazole (HPz) and l-phenyl-3-methylpyrazole (phmPz)} have been prepared and characterized by elemental analysis, i.r. and n.m.r. spectroscopy and by single crystal X-ray diffraction methods. The Pd atom in these structures lies on the crystallographic inversion center; in a square-planar coordination geometry made by two sulfur and two nitrogen atoms of the ligands, both in trans positions.

Light-induced electric dipole relaxation in synthetic and natural alexandrite

We present results of thermally stimulated depolarization current (TSDC) measurements in synthetic and natural alexandrite, which show TSDC bands related to the presence of electric dipoles in both types of samples. Synthetic material shows a wide TSDC band with a peak at 179 K, which can be fitted by two distinct relaxing dipole distributions. For natural alexandrite the TSDC band has a maximum around 195 K and can be fitted by three different distributions. Both samples present one of the calculated curves with a peak about 179 K, with activation energy of 0.57 eV and constant relaxation time of 1 × 10-14 sec. Photo-induced TSDC shows that TSDC bands can also be generated by simultaneous application of light and an electric field at 77 K.

Synthesis and spectroscopic characterization of a novel coordination polymer of palladium(II) with pyrazole and azido ligands

The one-dimensional coordination polymer of palladium(II) with pyrazolato (Pz -) and azide (N 3 -) as bridging ligands, of formula [Pd 3(μ-N 3)(μ-Pz) 5] n, has been prepared. From IR and Raman studies it was evidenced the exobidentate nature of pyrazole ligands as well the μ-1,1-bridging coordination of azido groups. NMR experiments showed two sets of broadened signals with different intensities indicating the presence of pyrazolato groups in distinct chemical environments. The proposed structure of [Pd 3(μ-N 3)(μ-Pz) 5] n consists of a zigzag ribbon in which each (Pz) 2Pd(Pz) 2 entity is bound to two stacked planar units [Pd(μ-Pz)(μ-N 3)Pd core] with very weak Pd-Pd interaction, based on UV-Vis spectroscopy.