Construção de campo de força empírico para estudo de complexos de Fe(III) com interesse bioinorgânico

In this work we present a new parametrization in molecular mechanics for studying iron complexes. This force field was implemented in the FORCES 2000 program, developed in our group for studying in coordination compounds of interest in bioinorganic chemistry. Mononuclear and dinuclear iron complexes were studied using this program with good success.

Fluidos supercríticos em química analítica. III.: aplicações

The first two papers in this series described the basic theory involved in supercritical fluid chromatography (SFC), how the technique evolved from gas and liquid chromatography and how the instrumentation was developed. Over the last two years, a commercial, dedicated packed-column SFC/MS instrument appeared on the market. The SFC continues to grow in use, with fundamental developments, coupled with a steady rise in the number of industrial users and applications.

Fenilsilicato dopado com Eu III obtido pelo método sol-gel

In this work, we report the synthesis and the photoluminescence features of a Eu(III)-doped modified silica matrix obtained by the sol-gel method. The matrix was prepared by reaction between tetraethylorthosilicate and phenyltriethoxysilane alkoxide. The hydrolysis occurred using basic catalysis. The solids were treated at 100, 200 and 300 ºC during 4 h and the structure was determined by thermogravimetric analysis (TG/DTG), nuclear magnetic resonance (NMR 29Si and 13C), infrared spectroscopy (IR) and photoluminescence (PL). The PL spectra display the Eu(III) lines characteristic of the ion, 5D0 -> 7F J (J=0, 1, 2, 3, 4), the blue emission as ascribed in the silica matrix. The NMR and TG showed the stability of hybrid silica.

Ciclização do lapachol induzida por sais de tálio III

This work describes the cyclization of lapachol (1) induced by thallium triacetate (TTA) and thallium trinitrate (TTN) in several solvents using magnetic stirring and under microwave irradiation. alpha-Xyloidone (2) - dehydro-alpha-lapachone - was obtained as the main product in these reactions in 20 75% yield. However, rhinacanthin-A (4) was isolated as main product in a 40% yield, using TTA and acetic anhydride:water (1:1) as solvent, and dehydro-iso-alpha-lapachone (3) in 21% yield, using TTA and dichloromethane as solvent. The reaction time decreased drastically under microwave conditions, but the yields of these reactions were not the expected.

Extração líquido-líquido de ferro(III) e titânio(IV) pelo ácido bis-(2-etil-hexil) fosfórico (D2EHPA) em meio de ácido sulfúrico

This work presents a study on the separation of Fe(III) and Ti(IV) from sulfuric acid leaching solutions of ilmenite (FeTiO3) using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K D) of the elements related to free acidity and concentration of Fe(III) and Ti(IV) were determined. Free acidity was changed from 3x10-2 to 11.88 mol L-1 and D2EHPA concentration was fixed at 1.5 mol L-1. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO2.

Adsorção de arsênio(V) pela quitosana ferro - III reticulada

The removal of As(V) by a crosslinked iron(III)-chitosan adsorbent was evaluated under various conditions. The adsorption capacity of CH-FeCL was around 54 mg/g of As(V). The kinetics of adsorption obeys a pseudo-first-order model with rate constants equal to 0.022, 0.028, and 0.033 min-1 at 15, 25 and 35 ºC respectively. Adsorption data were well described by the Langmuir model, although they could be modeled also by the Langmuir-Freundlich equation. The maximum adsorption capacity, calculated with the Langmuir model, was 127 mg g-1 of As(V). The inhibition by competing anions is dependant on their kind and valence.

Rejeito de mineração de carvão como adsorvente para remoção da acidez, Fe (III), Al (III) e Mn (II) em drenagem ácida

This study aimed the use of coal mining waste as a new adsorbent for H3O+ and removal of Al (III), Fe (III) and Mn (II) from acid mine drainage. Data from kinetic and equilibrium of the adsorption of H3O+ followed the pseudo second-order and Langmuir isotherm models. The maximum adsorption capacity of H3O+ was 316 mmol kg-1. The adsorbent removed 100% of Al (III), 100% of Fe (III) and 89% of Mn (II), suggesting its use as an alternative for the treatment of acid mine drainage.

Pré-concentração de Cr(III) e análise de especiação de cromo empregando montmorilonita saturada com íons potássio

The clay mineral montmorillonite-K10 (MT), treated under acidic medium and saturated with potassium ions (MTK), was employed in sorption and desorption studies aiming the preconcentration of Cr(III) and the speciation analysis of chromium. The sorption process of Cr(III) was close to 100%, suggesting that MTK was a good material for Cr(III) preconcentration, although, the maximum recovery in HNO3 solution was near 89%. On the other hand, Cr(VI) practically was not retained in MTK, suggesting this material as an appropriate mineral phase to be used in speciation analysis of chromium in aqueous medium.

Synthesis and characterization of Fe(III)-piperazine-derived complexes encapsulated in zeolite Y

Zeolite-encapsulated complexes have been widely applied in hydrocarbon oxidation catalysis. The "ship-in-a-bottle" encapsulation of iron(III) complexes containing piperazine and piperazine-derivative ligands in zeolite-Y is described. The flexible ligand methodology was employed and the efficiency and reproducibility of the procedure was investigated. The catalysts were characterized employing several techniques and the results indicate the presence of coordinated and uncoordinated iron(III) ions inside and outside the zeolitic cage.

Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments

The present paper focuses on improving chromium (III) uptake capacity of sugarcane bagasse through its chemical modification with citric acid and/or sodium hydroxide. The chemical modifications were confirmed by infrared spectroscopy, with an evident peak observed at 1730 cm-1, attributed to carbonyl groups. Equilibrium was reached after 24 h, and the kinetics followed the pseudo-second-order model. The highest chromium (III) maximum adsorption capacity (MAC) value was found when using sugarcane bagasse modified with sodium hydroxide and citric acid (58.00 mg g-1) giving a MAC value about three times greater (20.34 mg g-1) than for raw sugarcane bagasse.

Monitoring of praseodymium(III) ions in aqueous solutions, soil and sediment samples by a PVC membrane sensor based on a furan-triazole derivative

A furan-triazole derivative has been explored as an ionophore for preparation of a highly selective Pr(III) membrane sensor. The proposed sensor exhibits a Nernstian response for Pr(III) activity over a wide concentration range with a detection limit of 5.2×10-8 M. Its response is independent of pH of the solution in the range 3.0-8.8 and offers the advantages of fast response time. To investigate the analytical applicability of the sensor, it was applied successfully as an indicator electrode in potentiometric titration of Pr(III) solution and also in the direct and indirect determination of trace Pr(III) ions in some samples.

Síntese, caracterização e estudo das propriedades de um novo complexo mononuclear contendo quercetina e íon Ga(III)

Flavonoids are one of the most important compound groups applied as medicine given their antioxidant properties, but several intrinsic properties can be improved through structural modifications to their molecules. Here, the synthesis and characterization of a new gallium (III) complex with quercetin is described. Electrochemical properties, as well as antioxidant and cytotoxic activities, were investigated and compared to the free flavonoid molecule. The mononuclear complex obtained, [Ga(C15H9O7)3].2H2O.2CH3OH.CH3CH2OH, seems more active as a DPPH radical scavenger given its lower oxidation potential compared to quercetin. The new complex cytotoxic responses have shown to be more effective than those of the free flavonoid and of lapachol used as a control.

Determinação espectrofotométrica de sulfato em álcool etílico combustível empregando dibromosulfonazo III

A sensitive spectrophotometric method was developed for sulphate determination in automotive ethanol fuel. The method based on the reaction of the analyte with barium-dibromosulphonazo(III) complex lead to a decrease in the magnitude of the absorbance signals monitored at 649 nm. No sample pretreatment is required and the proposed method allows sulphate determination in the 0.45 - 6.50 mg L-1 range with R.S.D. < 2% and limit of detection of 0.14 mg L-1. The method has been successfully applied for sulphate determination in automotive ethanol fuel and the results agreed with the reference chromatographic method.

Preparation and immobilization of diNOsarcobalt(III) complex in zeolite y for the catalyzed production of hydrogen peroxide

A complex cation, diNOsarcobalt(III), [Co(diNOsar)]3+, (diNOsar = 1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo-[6.6.6]eicosane), was synthesized and immobilized in the cavities of a Y zeolite by the reaction of precursor species in the pores of the zeolite. The encapsulated material was compared to the compound diNOsarcobalt(III) chloride, [Co(diNOsar)]Cl3. Both diNOsarcobalt(III) chloride and the zeolite-encapsulated complex, [Co(diNOsar)]3+/zeolite, were obtained in high yield and characterized by ultraviolet-visible and infrared spectroscopy. X-ray diffraction demonstrated the incorporation of the complex cation into the pores of the zeolite. The catalytic production of hydrogen peroxide from oxygenated water confirmed the successful synthesis of the complex diNOsarcobalt(III) immobilized in the zeolite.

Experimento didático de quimiometria para planejamento de experimentos: avaliação das condições experimentais na determinação espectrofotométrica de ferro II com o-fenantrolina. Um tutorial, parte III

The objective of this manuscript is to describe a practical experiment that can be employed for teaching concepts related to design of experiments using Matlab or Octave computing environment to beginners, undergraduate and graduate students. The classical experiment for determination of Fe (II) using o-phenanthroline was selected because it is easy to understand, and all the required materials are readily available in most analytical laboratories. The approach used in this tutorial is divided in two steps: first, the students are introduced to the concept of multivariate effects, how to calculate and interpret them, and the construction and evaluation of a linear model to describe the experimental domain by using a 2³ factorial design. Second, an extension of the factorial design by adding axial points is described, thereby, providing a central composite design. The quadratic model is then introduced and used to build the response surface.