Mechanism of Trypanosoma cruzi death induced by Cratylia mollis seed lectin

Incubation of T. cruzi epimastigotes with the lectin Cramoll 1,4 in Ca(2+) containing medium led to agglutination and inhibition of cell proliferation. The lectin (50 A mu g/ml) induced plasma membrane permeabilization followed by Ca(2+) influx and mitochondrial Ca(2+) accumulation, a result that resembles the classical effect of digitonin. Cramoll 1,4 stimulated (five-fold) mitochondrial reactive oxygen species (ROS) production, significantly decreased the electrical mitochondrial membrane potential (Delta I(m)) and impaired ADP phosphorylation. The rate of uncoupled respiration in epimastigotes was not affected by Cramoll 1,4 plus Ca(2+) treatment, but oligomycin-induced resting respiration was 65% higher in treated cells than in controls. Experiments using T. cruzi mitochondrial fractions showed that, in contrast to digitonin, the lectin significantly decreased Delta I(m) by a mechanism sensitive to EGTA. In agreement with the results showing plasma membrane permeabilization and impairment of oxidative phosphorylation by the lectin, fluorescence microscopy experiments using propidium iodide revealed that Cramoll 1,4 induced epimastigotes death by necrosis.

Electronic Structure of the Ground and Low-Lying Electronic States of MoB and MoB(+)

Multiconfigurational second-order perturbation theory (CASSCF//CASPT2) and quadruple-zeta ANO-RCC basis sets were employed to investigate the ground and low-lying electronic states of MoB and MoB(+). Spectroscopic constants, potential energy curves, wavefunctions, Mulliken population analyses, and ionization energies are given. The ground state of MoB is of X(6)Pi symmetry (R(e) = 1.968 angstrom, omega(e) = 664 cm(-1), and mu = 2.7 D), giving rise to a Omega = 7/2 ground state after including spin-orbit coupling. For MoB(+), the ground state is computed to be of X(7)Sigma(+) symmetry (R(e) = 2.224 angstrom, omega(e) = 141 cm(-1), and mu = 1.2 D), with an adiabatic ionization energy of 7.19 eV and a vertical one of 7.53 eV. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111: 3362-3370, 2011

Activated Copper Cathodes as Sensors for Nitrite Analysis

The increased surface area of copper electrodes upon applying a suitable potential protocol was characterized by atomic force microscopy images. Scanning electrochemical microscopy was used to demonstrate the enhanced reactivity of the generated surface. The modified electrode showed excellent catalytic activity towards nitrite reduction in acidic medium (pH 2). This new platform was used in the development of a fast and simple voltammetric method for nitrite determination. Commercial and rainwater spiked samples were analyzed and the data showed an excellent agreement with those obtained with a reference spectrophotometric method (Griess reaction) at a confidence level of 95% (Student`s t-test).

Reactions of toluquinone - cyclopentadiene Diels -Alder epoxide adducts with nucleophiles under heterogeneous conditions

Toluquinone-cyclopentadiene Diels-Alder epoxide adducts react with sulfur and oxygen nucleophiles under heterogeneous conditions, leading to products resulting from the epoxide ring opening and from skeletal rearrangement, respectively. Pyrolysis of the sulfanyl adducts gave the new 3-sulfanyltoluquinones (1).

Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.

Application of Microelectrode Voltammetry to Study the Properties of Surfactant Solutions: Alkyltrimethylammonium Bromides

Microelectrode cyclic voltammetry (MV) has been employed to investigate the micellar properties of solutions of homologous alkyltrimethylammonium bromides, RMe(3)ABr, R = C(10), C(12), and C(14), in water and in the presence of added NaBr. The micellar self-diffusion coefficient was calculated from the limiting current for the reversible electron transfer of micelle-bound ferrocene. From the values of this property, other parameters were calculated, including the micellar hydrodynamic radius, RH, and aggregation number, N(agg); the latter was also theoretically calculated. We determined the values of the diffusion coefficient as a function of various experimental variables and observed the following trends: The diffusion coefficient decreases as a function of increasing surfactant concentration (no additional electrolyte added); it decreases as a function of increasing surfactant concentration at fixed NaBr concentration; and it shows a complex dependence (increase then decrease) on the NaBr concentration at a fixed RMe(3)ABr concentration. The value of the intermicellar interaction parameter decreases and then increases as a function of increasing NaBr concentration. These results are discussed in terms of intermicellar,interactions and the effect of NaBr on the micellar surface charge density and sphere-to-rod geometry change. The NaBr concentration required to induce the latter change increases rapidly as a function of decreasing the length of R: no geometry change was detected for C(10)Me(3)ABr. Values of N(agg) increase as I function of increasing the length of R and are in good agreement with both literature values and values that were calculated theoretically. Thus, MV is a convenient and simple technique for obtaining fundamental properties of surfactant solutions, including additive-induced changes of micellar parameters (N(agg)) and morphology changes.

Microbiopsies of Surface Dental Enamel as a Tool to Measure Body Lead Burden

Lead (Pb) poisoning is preventable but continues to be a public health problem in several countries. Measuring Pb in the surface dental enamel (SDE) using microbiopsies is a rapid, safe, and painless procedure. There are different protocols to perform these microbiopsies, but the reliability of dental enamel lead levels (DELL) determination is dependent upon biopsy depth (BD). It is established that DELL decrease from the outermost superficial layer to the inner layer of dental enamel. The aim of this study was to determine DELL obtained by two different microbiopsy techniques on SDE termed protocol I and protocol II. Two consecutive enamel layers were removed from the same subject group (n = 138) for both protocols. Protocol I consisted of a biopsied site with a diameter of 4 mm after the application of 10 l HCl for 35 s. Protocol II involved a biopsied site of 1.6 mm diameter after application of 5 l HCl for 20 s. The results demonstrated that there were no significant differences for BD and DELL between homologous teeth using protocol I. However, there was a significant difference between DELL in the first and second layers using both protocols. Further, the BD in protocol II overestimated DELL values. In conclusion, SDE analyzed by microbiopsy is a reliable biomarker in protocol I, but the chemical method to calculate BD in protocol II appeared to be inadequate for measurement of DELL. Thus, DELL could not be compared among studies that used different methodologies for SDE microbiopsies.

A renewable copper electrode as an amperometric flow detector for nitrate determination in mineral water and soft drink samples

A novel approach was developed for nitrate analysis in a FIA configuration with amperometric detection (E=-0.48 V). Sensitive and reproducible current measurements were achieved by using a copper electrode activated with a controlled potential protocol. The response of the FIA amperometric method was linear over the range from 0.1 to 2.5 mmol L(-1) nitrate with a detection limit of 4.2 mu mol L(-1) (S/N = 3). The repeatability of measurements was determined as 4.7% (n=9) at the best conditions (flow rate: 3.0 mL min(-1), sample volume: 150 mu L and nitrate concentration: 0.5 mmol L(-1)) with a sampling rate of 60 samples h(-1). The method was employed for the determination of nitrate in mineral water and soft drink samples and the results were in agreement with those obtained by using a recommended procedure. Studies towards a selective monitoring of nitrite were also performed in samples containing nitrate by carrying out measurements at a less negative potential (-0.20 V). (C) 2009 Elsevier B.V. All rights reserved.

Flow injection amperometric determination of hydrogen peroxide in household commercial products with a ruthenium oxide hexacyanoferrate modified electrode

Hydrogen peroxide was determined in oral antiseptic and bleach samples using a flow-injection system with amperometric detection. A glassy carbon electrode modified by electrochemical deposition of ruthenium oxide hexacyanoferrate was used as working electrode and a homemade Ag/AgCl (saturated KCl) electrode and a platinum wire were used as reference and counter electrodes, respectively. The electrocatalytic reduction process allowed the determination of hydrogen peroxide at 0.0 V. A linear relationship between the cathodic peak current and concentration of hydrogen peroxide was obtained in the range 10-5000 mu mol L(-1) with detection and quantification limits of 1.7 (S/N = 3) and 5.9 (S/N = 10) mu mol L(-1), respectively. The repeatability of the method was evaluated using a 500 mu mol L(-1) hydrogen peroxide solution, the value obtained being 1.6% (n = 14). A sampling rate of 112 samples h(-1) was achieved at optimised conditions. The method was employed for the quantification of hydrogen peroxide in two commercial samples and the results were in agreement with those obtained by using a recommended procedure.

Developing a fluorimetric sequential injection methodology to study adsorption/desorption of glyphosate on soil and sediment samples

This paper describes the development of a sequential injection method to automate the fluorimetric determination of glyphosate based on a first step of oxidation to glycine by hypochlorite at 48 degrees C, followed by reaction with the fluorogenic reagent o-phthaldialdehyde in presence of 2-mercaptoethanol in borate buffer (pH > 9) to produce a fluorescent 1-(2`-hydroxyethylthio)-2-N-alkylisoindole. The proposed method has a linear response for glyphosate concentrations between 0.25 and 25.0 mu mol L(-1), with limits of detection and quantification of 0.08 and 0.25 mu mol L(-1), respectively. The sampling rate of the method is 18 samples per hour, consuming only a fraction of reagents consumed by the chromatographic method based on the same chemistry. The method was applied to study adsorption/desorption properties in a soil and in a sediment sample. Adsorption and desorption isotherms were properly fitted by Freundlich and Langmuir equations, leading to adsorption capacities of 1384 +/- 26 and 295 +/- 30 mg kg(-1) for the soil and sediment samples, respectively. These values are consistent with the literature, with the larger adsorption capacity of the soil being explained by its larger content of clay minerals, while the sediment was predominantly sandy. (C) 2011 Elsevier B.V. All rights reserved.

Radical Scavenging Capacity of Piper arboreum and Piper tuberculatum (Piperaceae)

In the scope of our ongoing researchers on antioxidant compounds, twenty four extracts and fractions obtained from Piper arboreum Aublet and Piper tuberculatum Jacq. (Piperaceae) were screened for radical scavenging capacity (RSC) by using DPPH colorimetric assay. The strongest activity was found in ethyl acetate fractions from the leaves of P. arboreum IC(50) = 5.70 mu g/mL) and P. tuberculatum IC(50) = 8.40 mu g/mL). Hydromethanol fractions of the leaves of P. tuberculatum and P. arboreum showed moderate RSC, with values of IC(50) (mu g/mL) of 11.9 and 19.2, respectively. Additionally, a brief phytochemical study of the ethyl acetate fraction of P. arboreum leaves affording quercetin (1) and quercitrin (2), two flavonols with antioxidant activity previously described in the literature.

Triangular ruthenium acetate clusters containing the bis(pyridyl)propane ligand and their inclusion chemistry with beta-cyclodextrin

The triruthenium carboxylate cluster [Ru(3)O(OAc)(6)(py)(2)(bpp)](+) (OAc = acetate) containing the bridging 1,3-bis(4-pyridyl)propane (bpp) ligand, and its dimeric species [{Ru(3)O(OAc)(6)(py(2))}(2)(mu-bpp)](2+) were synthesized in order to investigate their inclusion compounds with beta-cyclodextrin (beta-CD). Characterization of the complexes was carried out based on spectroscopic, electrochemical and spectroelectrochemical techniques, while the formation of inclusion complexes was evaluated using (1)H NMR/NOESY spectroscopy. Since bpp is a flexible ligand, a DFT study was carried out in order to characterize its conformational isomers and their possible role in the host-guest chemistry with beta-CD. Instead of observing the formation of inclusion compounds with different stoichiometries, we observed the formation of 1:1 bpp/beta-CD compounds in which the bpp ligand assumes different conformations. The assembly of polymetallic rotaxane species was successfully demonstrated by monitoring the (1)H NMR spectra of the monomeric cluster species in the presence of aquapentacyanoferrate(II) ions and beta-CD.

Bacterial cellulose-laponite clay nanocomposites

A novel material comprised of bacterial cellulose (BC) and Laponite clay with different inorganic organic ratios (m/m) was prepared by the contact of never-dried membranes of BC with a previous dispersion of clay particles in water. Field emission scanning electron microscopy (FE-SEM) data of composite materials revealed an effective adhesion of clay over the surface of BC membrane; inorganic particles also penetrate into the polymer bulk, with a significant change of the surface topography even at 5% of clay loading. As a consequence, the mechanical properties are deeply affected by the presence of clay, increasing the values of the Young modulus and the tensile strength. However the maximum strain is decreased when the clay content is increased in the composite in comparison to pristine BC. The main weight loss step of the composites is shifted towards higher temperatures compared to BC, indicating that the clay particles slightly protect the polymer from thermal and oxidative decomposition. (C) 2010 Elsevier Ltd. All rights reserved.

Compatibility and decomposition kinetics studies of prednicarbate alone and associated with glyceryl stearate

In this work, TG/DTG and DSC techniques were used to the determination of thermal behavior of prednicarbate alone and associated with glyceryl stearate excipient ( 1: 1 physical mixture). TG/DTG curves obtained for the binary mixture showed a reduction of approximately 37 degrees C to the thermal stability of drug (T(dm/dt-0) (Max)(DTG)). The disappearance of stretching band at 1280 cm(-1) (nu(as) C-O, carbonate group) and the presence of streching band with less intensity at 1750 cm(-1) (nu(s) C-O, ester group) in IR spectrum obtained to the binary mixture submitted at 220 degrees C, when compared with IR spectrum of drug submitted to the same temperature, confirmed the chemical interaction between these substances due to heating. Kinetics parameters of decomposition reaction of prednicarbate were obtained using isothermal (Arrhenius equation) and non-isothermal (Ozawa) methods. The reduction of approximately 45% of activation energy value (E(a)) to the first step of thermal decomposition reaction of drug in the 1:1 (mass/mass) physical mixture was observed by both kinetics methods.

Excited-State Dynamics in fac-[Re(CO)(3)(Me(4)phen)(L)](+)

Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, 3IL(cis-L), (3)MLCT(Re -> me4phen), and (3)IL(Me4phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re -> Me4phen) and (3)IL(Me4phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (Delta E(a)) for interconversion between (3)MLCT(Re -> me4Phen) and (3)IL(Me4phen) emitting states were determined. For L = cis-stpy, Delta E(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, Delta E(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(me4phen) state to (3)MLCT(Re -> Me4phen), k(i) congruent to 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.