Digestão fotoquímica, assistida por microondas, de águas naturais: aplicação em estudos de partição e especiação do cobre

The efficiency of a new procedure for the digestion of natural waters, based on a microwave-activated photochemical reactor was evaluated in this work. Fluorescence spectra showed a 99% reduction in the emission of a 40 mg L-1 humic acid solution after 15 min of UV irradiation. In the presence of H2O2, only 3 min were necessary to accomplish a reduction of almost 100% in the emission and 6 min to reduce the concentration of dissolved organic carbon by 95%. The copper recovery from synthetic samples containing commercial humic acid, from soil suspensions, as well as from natural waters varied between 91.5 and 106.6%. The digestion of dissolved and unfiltered samples was successfully accomplished in 6 and 12 min, respectively. No contaminations or sample losses were observed. Results of copper speciation in natural waters showed that this metal is predominantly bound to natural ligands. Only 3-6% of the total recoverable copper is present in the labile form.

Hemes férricos pentacoordenados e hexacoordenados dos monômeros d nativo e reconstituído da hemoglobina extracelular de Glossoscolex paulistus: estudos espectroscópicos em meio ácido

UV-Vis and fluorescence spectroscopic studies of the native and reconstituted d monomers of Glossoscolex paulistus were performed in acid medium. The coexistence of distinct species shows the complexity of the equilibria. Besides the hexacoordinate low spin hemichrome, with bands at 535 and 565 nm, a pentacoordinate high spin hemichrome is identified by the blue-shifted low intensity Soret band (371 nm) and the LMCT band (643 nm). The pentacoordinate hemichrome must be related to the partial unfolding of the polypeptide.

Construção e estudos de perfomance de um reator fotoquímico tipo CPC ("Compound Parabolic Concentrator")

A CPC (Compound Parabolic Concentrator) reactor was projected and constructed aiming to promote the degradation of the organic matter present in considerable volumes of aqueous effluents, under the action of solar radiation. The essays were done using a model effluent which consists of a mixture of fragments of a sodium salt of lignosulphonic acid possessing a mean molecular weigth of 52,000 Daltons, and a real effluent, from a chip board industry. The volume of effluent in each test was about 50 L. The tests involved heterogeneous (TiO2 P25 Degussa and formulations made from the association of TiO2 with a photosensitiser), and homogeneous (thermal and photochemical Fenton reactions) catalysis of the effluents. The results demonstrate the viability of application of this kind of reactor even when the load of organic pollutants is high.

Estudos Cinéticos da aquação do trans-[Co(en)2Cl2]Cl

The trans-dichlorobis(ethylenediamine)cobalt(III) chloride was synthesized in an undergraduate laboratory and its aquation reaction was carried out at different temperatures. This reaction follows pseudo-first-order kinetics and the rate constants, determined at 25, 35, 45, 55 and 70 º C, are 1.44 x 10-3; 5.14 x 10-3; 1.48 x 10-2; 4.21 x 10-2 and 2.21 x 10-1 s-1, respectively. The activation energy is 93.99 ± 2.88 kJ mol-1.

Estudos de caso em química

The case-study method of instruction is increasing in popularity and instructors of various scientific disciplines are adopting this method for their courses. Its effectiveness suggests that there is a need for such resources to be used in chemistry education. In this paper we describe this method in detail and present our use of cases in a scientific communication course offered to undergraduate chemistry students at the University of São Paulo. The description of the method and the example of its use may be helpful for faculty members who wish to explore new ways to engage students more deeply in their learning and to reinvigorate their own teachig practice.

A rota dos estudos sobre a cochonilha em Portugal e no Brasil no século XIX: caminhos desencontrados

For imparting an intense and long-lasting red to fabrics, cochineal remained in high demand during the eighteenth and nineteenth centuries. This period witnessed, accordingly, several initiatives aimed at producing the precious dye: publication of specialized texts, cultivation of the cactus and the insect from which the dye is extracted, and, also, attempts to obtain the secrets of production through espionage. The present paper analyses certain aspects of the measures adopted by the Portuguese government towards Brazil in this field. The work shows how people sought to take part in the network of cochineal production (yet they were unsuccessful most of the time).

Estudos termoanalíticos de sais de sódio e potássio de ditiocarbamatos em atmosfera oxidante

Thermoanalytical behavior of sodium and potassium salts of pyrrolidinedithiocarbamate (pyr), piperidineditiocarbamate (pip), morpholinedithiocarbamate (mor), hexametileneiminedithiocarbamate (hex), were investigated. In a first step the salts were synthesized and characterized by infrared spectroscopy (FTIR), ¹H and 13C nuclear magnetic resonance (NMR) and elementar analysis. Finally, thermal analytical (TG/DTG and DSC) studies were performed in order to evaluate the thermal stability, as well as the pathways of the thermal decomposition based in the intermediate and final decomposition products.

Desenvolvimento e validação de um método analítico rápido por cromatografia líquida de alta eficiência para determinação de nimesulida em estudos de liberação in vitro

A high performance liquid chromatography (HPLC) method has been developed for a rapid determination of nimesulide in dissolution studies. Nimesulide was analyzed using 5 µm Lichrospher® RP-18 column (125 x 4 mm i.d.) and mobile phase acetonitrile: phosphate buffer pH=6.0 (55:45) at a flow-rate of 1.0 mL min-1. Detection was carried out at 300 nm at 25 ºC. The method was applied to analysis of nimesulide in in vitro release studies and showed a rapid and efficient analytical alternative for evaluation of dissolution profile of nimesulide.

Estudos espectroscópicos e estruturais dos polímeros de coordenação 2D, ∞[Tb(DPA)(HDPA)] e ∞[Gd(DPA)(HDPA)]

This paper presents the synthesis of the coordination polymers ∞[Ln(DPA)(HDPA)] (DPA=2,6-pyridinedicarboxylate; Ln= Tb and Gd), their structural and spectroscopic properties. The structural study reveals that the ∞[Ln(DPA)(HDPA)] has a single Ln+3 ion coordinated with two H2DPA ligands in tridentade coordination mode, while two others H2DPA establish a syn-bridge with a symmetry-related Ln3+, forming a two-dimensional structure. The spectroscopic studies show that ∞[Tb(DPA)(HDPA)] compound has high quantum yield (q x≈ 50.0%), due to the large contribution of radiative decay rate. Moreover triplet level is localized sufficiently over the emitter level 5D4 of theTb3+ ion, avoiding a retrotransference process between these states.

Estudos químicos e biológicos de Microgramma vacciniifolia (Langsd. & Fisch.) Copel (Polypodiaceae)

Chemical studies with aerial parts of Microgramma vacciniifolia (Langsd. & Fisch.) Copel. afforded ²-sitosterol, hopan-22-ol, 6-metoxiapinenin-7-O-²-D-allopyranoside and a mixture containing ethyl esters of carboxilic acids. The structures of the coumpounds were elucidated by spectroscopy and GC-MS analysis. The total phenolics contents of the crude extract and fractions were determined by Folin-Ciocalteau method. The antioxidant activity was evaluated using the 2,2-diphenyl-1-picrylhydrazyl (DPPH). The AcOEt fraction showed better activity in DPPH assay (9.9 ± 0.03 µg/mL), and presented also higher contents of the total phenolic (93.60 ± 1.11 µg/mg). Antimicrobial and allelopathic effects of the crude etanolic extract and fractions also were evaluated. In addition, the combination of biological activities was discussed.

Traçadores: o uso de agentes químicos para estudos hidrológicos, ambientais, petroquímicos e biológicos

This paper presents a revision of the history, definitions, and classification of tracers (natural and artificial, internal and external). The fundamental ideas concerning tracers are described, followed by their application illustrated by typical examples. The advantages and disadvantages of five classes among the most frequently used external tracers (fluorescent, microbial, chemical, radioactive and activable isotopes) are also described in detail. This review also presents some interesting and modern applications of tracers in the areas of diagnostics in medical practice, environmental pollution, hydrology and petroleum chemistry.

Líquido iônico [bmim.PF6] como solvente: um meio conveniente para estudos por fotólise por pulso de laser

The spectroscopic behavior of thioxanthone and benzil (diphenylethanedione or dibenzoyl) in the ionic liquid [bmim.PF6] has been investigated employing the laser flash photolysis technique. Triplet-triplet absorption spectra for these carbonyl compounds in [bmim.PF6] are similar to those observed in organic solvents. The triplet lifetime for thioxanthone in desogygenated samples is very long (71 μs), whereas in oxygen-saturated solution is 500 ns, which indicates the low oxygen solubility in this solvent. For benzil, lifetimes of 10 μs in [bmim.PF6] and 3.8 μs in acetonitrile were obtained. The decay for triplet thioxanthone and benzil follows a clear first order kinetics in [bmim.PF6], from which one can conclude that triplet-triplet annihilation is not an important decay process in this solvent.

Estudos de QSAR 3D para um conjunto de inibidores de butirilcolinesterase humana

Alzheimer's disease (AD) is considered the main cause of cognitive decline in adults. The available therapies for AD treatment seek to maintain the activity of cholinergic system through the inhibition of the enzyme acetylcholinesterase. However, butyrylcholinesterase (BuChE) can be considered an alternative target for AD treatment. Aiming at developing new BuChE inhibitors, robust QSAR 3D models with high predictive power were developed. The best model presents a good fit (r²=0.82, q²=0.76, with two PCs) and high predictive power (r²predict=0.88). Analysis of regression vector shows that steric properties have considerable importance to the inhibition of the BuChE.

Propriedades químico-quânticas empregadas em estudos das relações estrutura-atividade

In this work we show that structure-activity relationship studies are of great importance in modern chemistry and biochemistry. In order to obtain a significant correlation, it is crucial that appropriate descriptors be employed. Thus, quantum chemical calculations are an attractive source of new molecular descriptors which can, in principle, express all the electronic and geometric properties of molecules and their interactions with the biological receptor.

Síntese, caracterização e estudos de interação de um análogo da antitoxina CcdA empregando fluorescência no estado estacionário

Toxin-antitoxin (TA) systems contribute to plasmid stability by a mechanism called post-segregational killing. The ccd was the first TA system to be discovered with CcdB being the toxin and CcdA the antitoxin. CcdA, an 8.3 kDa protein, interacts with CcdB (11.7 kDa), preventing the cytotoxic activity of CcdB on the DNA gyrase. As an approach to understanding this interaction, CcdA41, a polypeptide derived from CcdA, was synthesized by solid-phase methodology and its interaction with CcdB was analyzed by steady state fluorescence. CcdA41 formed a stable complex with CcdBET2, a peptide based on CcdB, the more recently described bacterial topoisomerase inhibitor.