Ozonólise das ligninas organossolve e kraft eucalipto. Parte II: cinética nos meios ácido e básico

Organosolv and kraft lignins were treated with ozone both in basic and acid media and the reaction was studied kinetically. In contrast to reported studies, ozone was more efective in basic medium. Kraft lignin was degraded faster than organosolv lignin in both media but in the basic medium the rate of reaction was very much faster than in the acid one: for kraft lignin, the observed degradation was 93% for 2 min of reaction in the basic medium and 56% for 10 min of reaction in the acid medium; for organosolv lignin, 47% and 25%, respectively, in the same times. Higher phenolic hydroxyl groups contents increase the reaction rate.

Reações de inserção intramolecular de diazo compostos polifuncionais catalisadas por ródio(II): síntese de oxetan-3-ona-2-carboxilato e outros heterociclos funcionalizados

gamma-Hydroxy-alpha-diazo-beta-ketoesters are key intermediates in the chemistry of penicilin-based antibiotics and natural products. The method developed here for the synthesis of ethyl 2-diazo-4-hydroxy-3-oxo-butanoate 17 (in two steps from the diazo mercurial 2) compares very favorably with those reported in the literature for similar compounds. The Rh2(OAc)4-mediated intramolecular OH-insertion reaction of the diazo hydroxy ester 17 was investigated, furnishing the oxetan-3-one-2-carboxilate 18 in good yield. When the diazo ester lacks a free hydroxyl group as in the case of the phenoxy diazo ester 11 an intramolecular CH-insertion takes place, affording the 2H-chromene 20 in almost quantitative yield. The behavior of other functionalized diazo esters towards Rh2(OAc)4 was also investigated.

Unambiguous assessments of reaction paths for selected pericyclic reactions

Four commonplace concerted reactions are examined using (i) correlation diagrams, (ii) frontier molecular orbital analyses for transition states, (iii) Zimmerman-Dewar analyses for transition states and (iv) modified Zimmerman-Dewar analyses for transition states. Only the latter approach is consistently satisfactory.

Síntese e caracterização de novos compostos de coordenação de cobre (II) com ligantes não-simétricos N,O-doadores: contribuições para o sítio ativo da galactose oxidase

The reactions of four new unsymmetrical N,O-donor ligands, {H2BBPETEN= [N-(2-hydroxybenzyl) - N,N' - bis(2 methylpyridyl) -N'-(hydroxyethyl) ethylenodiamine], H3BPETEN=[N,N'- bis(2-hydroxybenzyl) -N- (2-methylpyridyl) -N'- (hydroxyethyl) ethylenodiamine], HTPETEN=[N,N,N'- tris(2-methylpyridyl) -N'- (hydroxyethyl) ethylenodiamine] and H3BIMETEN=[N,N'-(2-hydroxybenzyl)-N-(1-methylimidazol-2-il-methyl)-N'- (hydroxyethyl)ethylenodiamine]}, with Cu(II) salts afforded the following mononuclear compounds: [CuII(HBBPETEN)]ClO4, [CuII(H2BPETEN)]ClO4 , [CuII(HTPETEN)](PF6)2 and [CuII(H2BIMETEN)]ClO4 . All were characterized by EPR, electronic spectroscopy and electrochemistry. The four copper (II) compounds showed interesting electrochemistry properties. All presented an anodic wave that can be attributed to the Cu (I) oxide formation at the electrode surface, or to a Cu0 sediment at the same surface or yet, to Cu(I) -> Cu(II) oxidation process with coupled chemistry reaction, due to their irreversibility. Two of the complexes are described as interesting synthetic models for the active site of the metalloenzyme galactose oxidase.

Adsorção de íons cobre(II) pela quitosana usando coluna em sistema sob fluxo hidrodinâmico

The adsorption of Cu(II) ions from aqueous solution by chitosan using a column in a closed hydrodynamic flow system is described. The adsorption capacities as a function of contact time of copper(II) ions and chitosan were determined by varying the ionic strength, temperature and the flow of the metal solution. The Langmuir model reproduced the adsorption isothermal data better than the Freundlich model. The experimental kinetic data correlate properly with the second-order kinetic reaction for the whole set of experimental adsorption conditions. The rate constants exercise great influence on the time taken for equilibrium to be established by complexation or electrostatic interaction between the amino groups of chitosan and the metal.

Determinação condutométrica de captopril em formulações farmacêuticas utilizando sulfato de cobre(II) como titulante

A simple and rapid conductometric method for captopril determination using copper(II) sulphate solution as titrant was developed. The method was based on the chemical reaction between captopril and Cu(II) ions yielding a precipitate. The conductance of the solution was monitored as a function of the added volume of titrant. The method was applied with success for captopril determination in three pharmaceutical formulations. The relative standard deviation for six successive measurements was smaller than 0.5%. Recovery values from three samples, ranging from 97.7 to 103%, were obtained.

Reaction mixtures formed by nitrite and selected sulfa-drugs showed mutagenicity in acidic medium

Nitrite, which is present in preserved meat and can be produced in the oral cavity by reduction of nitrate taken from vegetables, could react in stomach with nitrosatable drugs, giving genotoxic-carcinogenic N-nitroso compounds (NOC). The mutagenicity of reaction mixtures formed by sodium nitrite and selected sulfa-drugs (sulfathiazole, HST; phtalylsulfathiazole, PhST; complex Co(II)-sulfathiazole, Co(II)-ST) in acidic medium was evaluated using the Salmonella typhimurium reverse mutation assay (Ames test), with TA98 and TA 100 strains. The reactions were carried out at room temperature, with a mole ratio [nitrite]/[sulfa-drug] > 1. The three reaction mixtures showed mutagenic effects in the considered range.

Determination of Ni(II) in metal alloys by spectrophotometry UV-Vis using dopasemiquinone

A spectrophotometric method was proposed for Ni(II) determination in alloys using a dopa-semiquinone (L-1) to form [Ni(II)(L1-)3]1-, ε = 9.3 x 10³ L mol-1 cm-1. The optimal conditions for the determination were: wavelength 590 nm, temperature 25 °C, reaction time 45 min and pH 7.5. The Beer's law was obeyed for nickel from 3.33 x 10-5 to 1.78 x 10-4 mol L-1. The method was applied to complex samples, such as inox, nickel-titanium and cobalt-chromium alloys. A study of the potential interferents revealed that Mn was the major interferent. The limit of detection and quantification were 2.88 x 10-5 mol L-1 and 3.06 x 10-5 mol L-1, respectively.

Síntese e caracterização estrutural do ligante isatina-3-(N4-benziltiossemicarbazona) e do seu complexo de mercúrio(II)

The reaction of 4-(phenyl)thiosemicarbazide with isatin yielded a new ligand, isatin-3-(N4-benzylthiosemicarbazone). Isatin-3-(N4-benzylthiosemicarbazone) deprotonated in ethanol/KOH reacts with an ethanolic solution of Hg(NO3)2 to give a mercury complex. The compounds were characterized by IR and X-ray single crystal structure determination. The X-ray studies revealed that the complex possesses a tetrahedral geometry with two deprotonated thiosemicarbazone ligands coordenated. The ligand and its mercury complex crystallize in the monoclinic (P2(1)/c) and triclinic (P-1) crystal system, respectively.

Activity and sulfur resistance of Rh(I) and Pd(II) complexes

Two complexes of Rh(I) and Pd(II) with chloride and tridecylamine ligands were obtained and characterized by Elementary Analysis and by XPS and FTIR spectroscopies. Complexes anchored on γ-Al2O3 were tested in the styrene semi-hydrogenation reaction carried out in the absence or presence of a sulfur poison. Although both low loaded catalysts were highly selective, the Pd(II) complex was three times more active than the Rh(I) complex. The rhodium complex was more sulfur resistant but less active than the palladium complex. Differences in conversion and sulfur resistance between both complexes could be related to electronic and/or geometric effects.

Síntese, caracterização e estudo das propriedades magnéticas de um polímero de coordenação contendo cobalto(II) e cobre(II)

This work describes the synthesis and characterization of two new compounds with ligand opy (N-(2-pyridyl)oxamate): the copper(II) precursor [Me4N]2[Cu(opy)2].5H2O and CoII CuII coordination polymer {[CoCu(opy)2]}n×4nH2O. This latter compound was obtained by reaction of [Me4N]2[Cu(opy)2].5H2O and CoCl2.6H2O in water. The heterobimetallic CoII CuII chain was characterized by elemental analysis, IR spectroscopy, thermogravimetry and magnetic measurements. Magnetic characterization revealed typical behavior of one-dimensional (1D) ferrimagnetic chain as shown in the curves of temperature (T) dependence of magnetic susceptibility (χM), in the form of χMT versus T, and dependence of magnetization (M) with applied field (H).

Syntheses, characterization and antifungal activity of tris(1,10-phenanthroline)iron(ii) bis(n-r-sulfonyldithiocarbimate)zincate(ii)

Four new compounds with the general formula [Fe(phen)3][Zn(RSO2N=CS2)2], where phen = 1,10-phenanthroline, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N=CS2K2) and tris(1,10-phenanthroline)iron(II) sulfate, with zinc(II) acetate dihydrate in dimethylformamide. The elemental analyses and the IR data were consistent with the formation of the expected complexes salts. The ¹H and 13C NMR spectra showed the signals for the cationic iron(II) complex and dithiocarbimate moieties. The molar conductance data were consistent with the 1:1 cation:anion complexes in 1-4. The antifungal activities of the compounds were tested in vitro against Candida albicans, Candida tropicalis and Colletotrichum gloeosporioides.

Impregnação do ácido 12-tungstofosfórico em sílica - parte II: efeito de diferentes solventes na impregnação e atividade catalítica na esterificação metílica de ácido esteárico

Materials obtained by the immobilization of 12-tungstophosphoric acid (PTA) on silica using the method of impregnation with excess solution in distinct solvents (aqueous HCl, methanol:H2O, and acetonitrile) were evaluated for use as catalysts in the methyl esterification of stearic acid. Optimum conditions were established for the impregnation of 0.5 g (w/w) of PTA on amorphous silica, under stirring at 150 rpm for 24 h, using 20 mL of 0.1 mol L-1 HCl as the solvent. After calcination at 200 ºC, high conversions were obtained under mild reaction conditions, resulting in high turnover numbers. The catalyst was evaluated in ten catalytic cycles of use, where the activity was reduced only slightly, attesting its stability and the possibility to apply it to industrial production of methylesters.

Determinação espectrofotométrica indireta de capsaicinoides em pimentas Capsicum a partir da reação com o complexo de Co(II) com 4-(2-piridilazo) resorcinol

Capsaicinoids (CAPS) are substances responsible for pungency in Capsicum. It is important to quantify these types of compounds owing to their broad application in food, pharmaceuticals, cosmetics and chemical weapons. In this work, we developed an indirect spectrophotometric method based on the colorimetric reaction between CAPS, Co(II) 3.10×10-5 mol L-1 and 4-(2-pyridylazo) resorcinol (PAR) 6.23×10-5 and, in cachaça:water 92:8v/v solutions, for quantification of total CAPS in Capsicum peppers. The product of the reaction is CoPAR2CAPS2 and its absorption in aquo-ethanolic solution at 510 nm is proportional to the total CAPS concentration from 0.60 to 17.94 mg L-1. The values of limit of detection and limit of quantification were 0.0004 and 0.001 mg of CAPS/g of pepper, respectively, with 4% relative standard deviation. The developed method yielded similar results to those obtained from high performance liquid chromatography, with 95% of confidence.

Crystal structures of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Zn(II)

The crystal and molecular structures of [bis(5-chloro-2-methoxybenzoate)tetraaquamanganese(II)], [pentaaqua(5-chloro-2-methoxybenzoato)cobalt(II)] (5-chloro-2-methoxybenzoate), [pentaaqua(5-chloro-2-methoxybenzoato)nickel(II)] (5-chloro-2-methoxybenzoate) and [aquabis(5-chloro-2-methoxybenzoate)zinc(II)] monohydrate were determined by a single-crystal X-ray analysis. Mn(H2O)4L2 (where L = C8H6ClO3) crystallizes in the monoclinic system, space group P21/c. [Co(H2O)5L]L and [Ni(H2O)5L]L both are isostructural, space group P212121. The crystals of [Zn(H2O)L2] H2O are monoclinic, space group Pc. Mn(II) ion is positioned at the crystallographic symmetry center. Mn(II) and Co(II) ions adopt the distorted octahedral coordination but Zn(II) tetrahedral one.The carboxylate groups in the complexes with M(II) cations function as monodentate, bidentate and/or free COO-groups. The ligands exist in the crystals as aquaanions. The complexes of 5-chloro-2-methoxybenzoates with Mn(II), Co(II) and Zn(II) form bilayer structure.