Estudo semi-empírico de ácidos hidroxâmicos: ácido formoidroxâmico e derivados do aleloquímico dimboa

Open chain hydroxamic acid (Hx) can exist as Z and E diastereomers of two tautomers, hydroxamic acid and hydroximic acid. The conformational stability of the formohydroxamic acid isomers evaluated by PM3 compared better to ab initio results from the literature than AM1 results. Structural data of the cyclic Hx 2,4-dihydroxy-7-metoxy-2H-1,4-benzoxazin-3(4 H)-one (DIMBOA) obtained by both semiempirical methods compared well to ab initio results. pKa data from the literature for derivatives of the aldolic isomer of DIMBOA were compared to the stability of the anions resulting from the loss of protons of their phenol and hydroxamic acid groups, determined as the difference in heat of formation between anionic and neutral forms, calculated by AM1 and PM3 methods. Good correlations between theoretical and experimental data were obtained for both semiempirical methods.

Modificação de zeólitas para uso em catálise

The use of zeolites and other molecular sieves as catalysts is discussed at an introductory level. The text includes a brief historic background on the use of zeolites in catalysis, and a discussion of some chemical and physical properties of silicalite, aluminosilicate, and aluminophosphate molecular sieves. The strategies currently used to chemically modify zeolites and related materials to produce catalysts with increased activity and selectivity are discussed, including the use of redox molecular sieves for hydrocarbon oxidation and the leaching of the active metals from the support.

Estudo da degradação do herbicida ácido 2,4- diclorofenoxiacético (2,4-D) por meio da radiação gama do cobalto-60 em solução aquosa contendo ácido húmico

The use of pesticides in agriculture presents some problems to ecosytems as a consequence of their remaining in the environment. Conventional methods for environmental decontamination sometimes just transfer these residues from one place to another. The use of gamma radiation from cobalt-60 to induce 2,4-D degradation in aqueous solution containing humic acid was studied. Results show that the herbicide is completely degraded after treatment with a 30 kGy dose. There were decreases in the degradation of the 2,4-D when humic acid was added at all doses. Some radiolytic products are proposed. The 2,4-D radiolytic yields (G) from 2,4-D were calculated.

Danos ao DNA promovidos por ácido 5-aminolevulínico: possível associação com o desenvolvimento de carcinoma hepatocelular em portadores de porfiria aguda intermitente

5-Aminolevulinic acid (ALA) is a heme precursor accumulated in acute intermittent porphyria (AIP), which might be associated with hepatocellular carcinoma (HCC) in symptomatic patients. Under metal catalyzed oxidation, ALA and its cyclic dimerization product, 3,6-dihydropyrazine-2,5-dipropanoic acid, produce reactive oxygen species that damage plasmid and calf thymus DNA bases, increase the steady state level of 8-oxo-7,8-dihydro-2´-deoxyguanosine in liver DNA and promote mitochondrial DNA damage. The final product of ALA, 4,5-dioxovaleric acid (DOVA), is able to alkylate guanine moieties, producing adducts. ALA and DOVA are mutagenic in bacteria. This review shows an up-to-date literature data that reinforce the hypothesis that the DNA damage induced by ALA may be associated with the development of HCC in AIP patients.

Tendências em modificação de eletrodos amperométricos para aplicações eletroanalíticas

The most relevant advances on the analytical applications of chemically modified electrodes (CME) are presented. CME have received great attention due to the possibility of electrode surface modification including chemisorption, composite generation and polymer coating. In recent years, the interest in CME has increased overall to improve the sensitivity and selectivity of the electroanalytical probes, considering the electron mediator incorporation and the new conducting polymers development. The general procedures employed for the electrode modification and the operational characteristics of some electrochemical sensors are discussed.

Breve revisão de métodos de determinação de resíduos do herbicida ácido 2,4-diclorofenoxiacético (2,4-D)

This paper supplies a revision about the main techniques of extraction, clean-up and pre-concentration of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in water and soil samples, as well as chromatographic methods and immune assays for its identification and quantification.

Síntese e avaliação da atividade fitotóxica de novos análogos oxigenados do ácido helmintospórico

Several compounds related to helminthosporic acid (3) were synthesized via the [3+4] cycloaddition. The reaction of 3-hydroxymethyl-2-methylfuran (12) with 1,1,3,3-tetrabromo-4-methylpentan-2-one (13) resulted in 7-hydroxymethyl-4alpha-isopropyl-1alpha-methyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (8) (37%) and 7-hydroxymethyl-2alpha-isopropyl-1alpha-methyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (14) (12%), which were converted into 7-formyl-4alpha-isopropyl-1alpha-methyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (16) (32% from 8) and 7-formyl-2alpha-isopropyl-1alpha-methyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (18) (40% from 14), respectively. Reduction of (8) resulted in 7-hydroxymethyl-4alpha-isopropyl-1alpha-methyl-8-oxabicyclo[3.2.1]oct-6 -en-3alpha-ol (11) (63% from 8) and 7-hydroxymethyl-4alpha-isopropyl-1alpha-methyl-8-oxabicyclo[3.2.1]oct-6-en-3 beta-ol (15) (30% from 8). The 4alpha-isopropyl-1alpha-methyl-3-oxo-8-oxabicyclo[3.2.1]oct-6-en-7-oic acid (19) was obtained by oxidation of (16) (78%). The results of biological tests are described in details. The best result was observed for compound (15) that caused 76% inhibition on the root growth of D. tortuosum.

Aplicação da CLAE para determinação do ácido 10-Hidróxi-2-decenóico (10-HDA) em geléia real pura e adicionada a mel brasileiro

The aim of this paper was to determine the 10-HDA in pure royal jelly and products containing royal jelly, using HPLC methodology. 10-HDA is the natural indicator of the presence of royal jelly in products and also gives the authenticity of pure royal jelly. The chromatographic conditions used were: isocratic system, C18-H column, auto sampler, diode array UV-VIS detector (225 nm), mobile phase with methanol/water (45:55), pH= 2.5 and a-naphtol as internal standard. The results obtained using laboratory samples for pure royal jelly were 2.37%, varying from 0.15% for honey with 10% of royal jelly to 2.10% for honey with 90% of royal jelly respectivelly. For commercial products, the 10-HDA content varied from no detectable to 0.026%. The recovery test presented a minumum of 100.44% The detection limit was 45.92 ng/mL and the quantification limit was 76.53 ng/mL.

Métodos de preparação e atividade biológica do ácido quinolínico e derivados

In 1981 2,3-pyridine dicarboxylic acid (quinolinic acid) was discovery to be a selective agonist for the N-methyl -D-aspartic acid (NMDA) receptor. As a consequence it possesses neurotoxic activity resulting from overstimulation of the receptor. Quinolinic acid is implicated as an etiological factor in a range of neurodegenerative disease including AIDS related dementia, Huntington´s disease and Lyme disease. In the design of novel therapies to treat these diseases, some molecules have been identified as an important target. In this paper we described different methods to prepare quinolinic acid and derivatives.

Determinação de tanino em pedúnculo de caju: método da vanilina versus método do butanol ácido

To improve tannin assay in cashew apple, several parameters were examined, including (1) extraction solvents, (2) effects of water and boiling time on butanol acid reaction and (3) correlation between vanillin and butanol acid assay of tannin in cashew apples. The 50-70% acetone extracted the greatest amount of tannin from cashew apples. Concentrations of water in butanol reagents were adjusted and boiling time of butanol reaction was reduced at 15 min. Tannin of unripe cashew apples was purified on Sephadex LH-20, aiming to obtain tannin standard for butanol assay. The vanillin assay presented high correlation with the butanol acid assay.

Modificação de óleos e gorduras por biotransformação

The oleochemical industry has a permanent interested in controlling the physical, functional and organoleptical properties of their products and in producing useful derivatives from their raw materials. The potential of biotechnology for developing novel or well-known products at more competitive costs meets the need of this industrial segment in expanding their goals. In this work some technical aspects, problems and perspectives related to the production of oil and fat derivatives using biotransformation techniques are discussed. Particular emphasis is given to the description of biotransformation processes using lipase as catalyst, in view of the great versatility of this enzyme class to mediate typical reactions in this technological sector.

Comportamento da atomização eletrotérmica de ouro, prata, bismuto, cádmio, chumbo e estanho em soluções aquosas e em etanol, a partir de diferentes superfícies atomizadoras

The atomization behavior of Au, Ag, Bi, Cd, Pb, and Sn from pyrolitic graphite coating (L'vov platform) with the use Pd and Mg solutions, and zirconium coated platform with the analytes in nitric acid 0.2% v/v and in ethanol was investigated. In ethanol medium, the sensitivity gain was three-fold for Bi and Cd using Zr as modifier. Without modifier, the ethanol medium is appropriate only for Au and Cd. In nitric acid medium, the Zr coated platform elevates sensitivity at least two-fold for Bi and Cd. The method was applied to the determination of Ag, Au and Bi of certified steel samples, after on-line preconcentration, sorption on a minicolumn filled with C-18 bonded to silica gel and elution with ethanol. The concentrations obtained agreed with the recommended values.

Métodos para análise de ácido clorogênico

This paper describes the analytical methods for determination of total chlorogenic acid (CGA) and their individual isomers. Spectrofotometric methods are adequate for total CGA analysis in green coffee but they can provide inflated results for coffee products. High pressure liquid chromatography (HPLC) with gel permeation column and ultraviolet (UV) monitoring is adequate for the simultaneous analysis of total CGA, alkaloids and sugars in coffee products. HPLC-UV-reversed phase is a simple, rapid and precise method for the determination of the individual isomers of CGA. Gas chromatography (GC) also is applied to the analysis of the individual isomers but phenolic acids need to be derivatized before analysis. Both HPLC- and GC-mass spectrometry provide an unequivocal identification of the individual isomers. The capillary electrophoresis method is simple, rapid and adequate to the simultaneous analysis of polyphenols and xanthines. Advantages and limitations of each method are discussed throughout the text.

Aplicação e modificação química da sílica gel obtida de areia

The silica gel was obtained from sand and its surface was modified with POCl3 to produce Si-Cl bonds on the silica surface. Ethylenediamine was covalently bonded onto the chlorinated silica surface. The adsorption of the chlorides of divalent cobalt, nickel and copper was qualitatively studied to show that the bonding of ethylenediamine onto the silica gel surface produces a solid base capable of chelating metal ions from solution. The experiments illustrate the extraction of silica gel, its reactivity, the development of modified surfaces and its application in removing metal ions from water and are deigned for undergraduate inorganic chemistry laboratories.

Efeito do teor metálico em catalisadores Co/Al2O3 aplicados à reação de reforma a vapor de etanol

The development of cobalt catalysts to produce hydrogen from ethanol is the goal of this investigation. Co/Al2O3 catalysts were prepared by impregnation and characterized by atomic absorption, nitrogen adsorption, X-ray diffraction, Raman spectroscopy, temperature programmed reduction and carbon analysis. The catalysts contained Co3O4 oxide and Co3+ and Co2+ species interacting with alumina. The cobalt load affects the crystal size and the crystalline structure and higher Co loads influence the reaction mechanism, changing the selectivity of the catalysts, decreasing the amount of CO produced and avoiding the formation of products catalyzed by the support. The ethanol conversion was 50-70% with 10-<1% of CO in the hydrogen.