Synthesis, characterization and thermal behaviour of solid-state compounds of benzoates with some bivalent transition metal ions

Solid-state MBz compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu and Zn and Bz is benzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The procedure used in the preparation of the compounds via reaction of basic carbonates with benzoic acid is not efficient in eliminating excess acid. However the TG-DTA curves permitted to verify that the binary compounds can be obtained by thermosynthesis, because the benzoic acid can be eliminated before the thermal decomposition of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition and structure of the isolated compounds. On heating, these compounds decompose in two (Mn, Co, Ni, Zn) or three (Fe, Cu) steps with formation of the respective oxide (Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO) as final residue. The theoretical and experimental spectroscopic studies suggest a covalent bidentate bond between ligand and metallic center.

Electrical and magnetic properties of new compounds of the conductor anion [Ni(dmit)2]- and nitronyl nitroxide magnetic radicals

Three compounds have been synthesized with formulae [3-MeRad][Ni(dmit)2] (1), [4-MeRad][Ni(dmit)2] (2) and [4-PrRad][Ni(dmit)2] (3) where [Ni(dmit)2]- is an anionic pi-radical (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) and [3-MeRad]+ is 3-N-methylpyridinium alpha-nitronyl nitroxide, [4-MeRad]+ is 4-N-methylpyridinium alpha-nitronyl nitroxide and [4-PrRad]+ is 4-N-propylpyridinium alpha-nitronyl nitroxide. The temperature-dependent magnetic susceptibility of 1 revealed that an antiferromagnetic interaction operates between the 3-MeRad+ radical cations with exchange coupling constants of J1 = - 1.72 cm-1 and antiferromagnetism assigned to the spin ladder chains of the Ni(dmit)2 radical anions. Compound 1 exhibits semiconducting behavior and 3 presents capacitor behavior in the temperature range studied (4 - 300 K).

Teores de carbamato de etila e outros componentes secundários em diferentes cachaças produzidas em três regiões do estado de Minas Gerais: Zona da mata, sul de minas e vale do jequitinhonha

Minas Gerais is the highest producer of handmade spirits. Research has been carried out aiming to contribute to progress. Thus, the goal of this work is to evaluate the quality of spirits in three different regions of Minas Gerais state. We analyzed ethyl carbamate, alcoholic grade, volatile acidity, higher alcohols, aldehyde, esters, methanol, furfural and copper. The values obtained for ethyl carbamate varied from undetectable to 643.5 µg L-1, with only one region not following the legislation (150 µg L-1). Most of the compounds in the spirits were present within the limits estabilished by the legislation.

Larock Reaction in the synthesis of heterocyclic compounds

The indole ring is one of the most common features in natural products and small molecules with important bioactivity. Larock reported a new methodology for the synthesis of the indole ring system based on the palladium-catalyzed heteroannulation of 2-iodoaniline and substituted alkyne moieties. This procedure was subsequently extended to the preparation of other nitrogen- and oxygen- containing heterocycles. This is the process of choice for the synthesis of a large number of heterocyclic derivatives, as it provides outstanding regioselectivity and good to excellent yields.

Antimycobacterial and cytotoxicity activity of synthetic and natural compounds

Antimycobacterial and cytotoxicity activity of synthetic and natural compounds. Secondary metabolites from Curvularia eragrostidis and Drechslera dematioidea, Clusia sp. floral resin, alkaloids from Pilocarpus alatus, salicylideneanilines, piperidine amides, the amine 1-cinnamylpiperazine and chiral pyridinium salts were assayed on Mycobacterium tuberculosis H37Rv. N-(salicylidene)-2-hydroxyaniline was the most effective compound with a minimal inhibitory concentration (MIC) of 8 µmol/L. Dihydrocurvularin was moderately effective with a MIC of 40 µmol/L. Clusia sp. floral resin and a gallocatechin-epigallocatechin mixture showed MIC of 0.02 g/L and 38 µmol/L, respectively. The cytotoxicity was evaluated for N-(salicylidene)-2-hydroxyaniline, curvularin, dihydrocurvularin and Clusia sp. floral resin, and the selectivity indexes were > 125, 0.47, 0.75 and 5, respectively.

Larock Reaction in the synthesis of heterocyclic compounds

The indole ring is one of the most common features in natural products and small molecules with important bioactivity. Larock reported a new methodology for the synthesis of the indole ring system based on the palladium-catalyzed heteroannulation of 2-iodoaniline and substituted alkyne moieties. This procedure was subsequently extended to the preparation of other nitrogen- and oxygen- containing heterocycles. This is the process of choice for the synthesis of a large number of heterocyclic derivatives, as it provides outstanding regioselectivity and good to excellent yields.

Cloud point extraction for the determination of copper in environmental samples by flame atomic absorption spectrometry

A simple cloud point extraction procedure is presented for the preconcentration of copper in various samples. After complexation by 4-hydroxy-2-mercapto-6-propylpyrimidine (PTU), copper ions are quantitatively extracted into the phase rich in Triton X-114 after centrifugation. Methanol acidified with 0.5 mol L-1 HNO3 was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). Analytical parameters including concentrations for PTU, Triton X-114 and HNO3, bath temperature, centrifugation rate and time were optimized. The influences of the matrix ions on the recoveries of copper ions were investigated. The detection limits (3SDb/m, n=4) of 1.6 ng mL-1 along with enrichment factors of 30 for Cu were achieved. The proposed procedure was applied to the analysis of environmental samples.

Processos avançados de oxidação de compostos fenólicos em efluentes industriais

In an effort to minimize the impact on the environment, removal of pollutants, such as phenolic compounds, from the industrial wastewater has great importance nowadays because of the high toxicity and low biodegradability of these compounds. This work discusses the different methods to remove these compounds from industrial wastewater, showing their advantages and disadvantages. Advanced Oxidation Process (AOPs) are presented as a promising technology for the treatment of wastewater containing phenolic compounds. Among the AOPs, photolysis, photocatalysis and the processes based on hydrogen peroxide and on ozone are discussed with emphasis on the combined processes and the oxidation mechanisms.

Isolation of compounds attractive to the leaf-cutting ant Atta sexdens rubropilosa forel (hymenoptera: Formicidae) from Mabea fistulifera elaiosome

Mabea fistulifera (Euphorbiaceae)is a pioneer plant species with seeds dispersed by the ant Atta sexdens rubropilosa. Since the ants are attracted to the seeds to use its elaiosome as a source of energy, we investigated its composition. The elaiosomes from 13,000 seeds were extracted with a methanol:chloroform mixture (2:1 v/v) and yielded 22% of a residue. This residue was fractionated by column chromatography and its composition determined by infrared spectroscopy and chromatography/mass spectrometry (GC-MS). The elaiosome lipids are constituted mainly by free fatty acids, triacylglycerols and minor quantities of monoacylglycerols or diacylglycerols.

Plasma polymerized acetaldehyde thin films for retention of volatile organic compounds

The aim of this work is the production and characterization of plasma polymerized acetaldehyde thin films. These films show highly polar species, are hydrophilic, organophilic and easily adsorb organic reactants with CO radicals but only allow permeation of reactants with OH radicals. The good step coverage of films deposited on aluminum trenches is useful for sensor development. Films deposited on hydrophobic substrates may result in a discontinued layer, which allows the use of preconcentration in sample pretreatment. Deposition on microchannels showed the possibility of chromatographic columns and/or retention system production to selectively detect or remove organic compounds from gas flows.

Volatile compounds in the thermoplastic extrusion of bovine rumen

The volatile compounds of raw and extruded bovine rumen, extracted by dynamic headspace, were separated by gas chromatography and analyzed by GC-MS. Raw and extruded materials presented thirty-two volatile compounds. The following compounds were identified in raw bovine rumen: heptane, 1-heptene, 4-methyl-2-pentanone, toluene, hexanal, ethyl butyrate, o-xylene, m-xylene, p-xylene, heptanal, limonene, nonanal, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane. The following compounds were identified in the extruded material: 1-heptene, 2,4-dimethylhexane, toluene, limonene, undecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane and nonadecane. Mass spectra of some unidentified compounds indicated the presence of hydrocarbons with branched chains or cyclic structure.

Ambiental volatile organic compounds in the megacity of São Paulo

In order to characterize the composition of the main urban air organic compounds in the megacity of Sao Paulo, analysis of samples collected during the winter of 2003 downtown was carried out. The samplings were performed on the roof of a building in the commercial center of São Paulo. Hydrocarbons and carbonyls compounds were collected on August 4, 5 and 6. Comparing to previous data, the concentration of hydrocarbons presented no decrease in the concentration, except for the aldehydes, which decreased when compared to previous data. Among the HCs species analyzed, the highest concentrations observed were those of toluene (7.5 ± 3.4 ppbv), n-decane (3.2 ± 2.0 ppbv), benzene (2.7 ± 1.4 ppbv) and 1,3,5-trimethylbenzene (2.2 ± 1.5 ppbv).

Estudo do comportamento eletroquímico de substâncias complexantes utilizando eletrodo de cobre

Copper electrode can be used for determination of complexing compounds through complexation reactions between Cu(II) and the analites. In this work some studies with three compounds were performed: glycine (precursor of glyphosate synthesis), herbicide glyphosate and aminomethylphosphonic acid (main metabolite of glyphosate). These compounds are complexing agents for Cu electrodes. Through simple experiments (cyclic voltammetry and corrosion studies) the applicability of the copper electrode as electrochemical sensor for complexing compounds in flow systems was presented.

Volatile compounds of Nectandra salicina (lauraceae) from Costa Rica and their cytotoxic activity on cell lines

The chemical composition of the volatiles of Nectandra salicina growing wild in Costa Rica was determined by capillary GC/FID and GC/MS. Thirty-seven and forty-two compounds were identified in the leaf and branch oils respectively corresponding to about 92.6 and 86.2% of the total amount of the oils. The major components of the leaf oil were: atractylone (14.6%), viridiflorene (10.1%), α-pinene (9.4%), β-caryophyllene (7.2%), α-humulene (7.0%), δ-cadinene (6.1%), β-pinene (6.0%) and germacrene D (5.8%). The major components of the branch oil were: atractylone (21.1%), germacrene D (10.7%), viridiflorene (7.9%) and 7-epi-α-selinene (5.0%). When the oils were tested on different cell lines, all the LD50 values were higher than 150 µg/mL, with values very similar for the leaf and branch oils. Low toxicity could be explained by antagonistic effects among the main compounds present in the oils.

Efeito de substâncias empregadas para remoção de cobre sobre o teor de compostos secundários da cachaça

High copper content is of great concern among producers of sugar-cane spirits who frequently use filters instead of cleaning the stills. This study compared the efficiency of activated carbon, ion-exchange-polymeric resin, and activated-carbon/iron-oxide magnetic composite for copper reduction without removing excessive organic compounds that are important for the beverage's quality. Resin was the most efficient copper adsorbent, removing fewer organic compounds. The composite also removed copper; however, it also removed large amounts of organic compounds. Activated carbon didn't remove sufficient copper to reduce its concentration to less than 5 g L-1, and it removed large amounts of higher alcohols and esters.