Electrocatalysis of reduced L-glutathione oxidation by iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) adsorbed on multi-walled carbon nanotubes

The development of a highly sensitive voltammetric sensor for reduced l-glutathione (GSH) using a basal plane pyrolytic graphite (BPPG) electrode modified with iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) adsorbed on multi-walled carbon nanotubes (MWCNT) is described. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were used to verify the morphologies and composition of the MWCNT after modification with the FeT4MPyP complex. The modified electrode showed very efficient electrocatalytic activity for l-glutathione oxidation, substantially decreasing the oxidation peak to -0.025V vs Ag/AgCl. A linear response range from 5 micromolL(-1) to 5 mmolL(-1) was obtained with a sensitivity of 703.41 microALmmol(-1). The detection limit for GSH determination was 0.5 micromolL(-1) and the relative standard deviation (R.S.D.) for 10 determinations of 250 micromolL(-1) GSH was 1.4%. The modified electrode was applied for GSH determination in erythrocyte samples and the results were in agreement to those obtained by a comparative method described in the literature.     

Extension of the MST continuum solvation model to the RM1 semiempirical Hamiltonian

The need to simulate large-sized molecules or to deal with large series of compounds is a challenging topic in computational chemistry, which has stimulated the development of accurate semiempirical methods, such as the recently reported Recife Model 1 (RM1; J Comput Chem 2006, 27, 1101). Even though RM1 may prove to be of value simply due to the enhanced quantitative accuracy in gas phase, it is unclear how the new parameters optimized for RM1 affect the suitability of this semiempirical Hamiltonian to study chemical processes in condensed phases. To address this question, we report the parametrization of the MST/RM1 continuum model for neutral solutes in water, octanol, chloroform and carbon tetrachloride, and for ions in water. The results are used to discuss the transferability of the solvation parameters implemented in previous MST/AM1 and MST/PM3 models.     

Methods and Supports for Immobilization and Stabilization of Cyclomaltodextrin Glucanotransferase from Thermoanaerobacter

Thermoanaerobacter cyclomaltodextrin glucanotransferase (CGTase) was immobilized using different supports and immobilization methods to study the effect on activity recovery. The enzyme covalently attached into glyoxyl-silica showed low activity recovery of 1.5%. The hydrophobic adsorption of the enzyme on Octadecyl-Sepabeads yielded also low activity recovery, 3.83%, and the enzyme could easily leak from the support at low ionic strength, although the immobilization yield was satisfactory, approximately 76%. The CGTase encapsulated in a sol–gel matrix gave an activity recovery of 6.94% and maximum cyclization activity at 60 °C, at pH 6.0. The half-time life at 60 °C, pH 6.0, in the presence of substrate was 100 min, which was lower than that of the free enzyme. The best activity recovery in this work (6.94%) is approximately five times smaller than that obtained previously using glyoxyl-agarose as support and covalent immobilization. Thus, the best support and method we tested so far for immobilization of CGTase is covalent attachment on glyoxyl-agarose.     

A highly sensitive amperometric sensor for oxygen based on iron(II) tetrasulfonated phthalocyanine and iron(III) tetra-(N-methyl-pyridyl)-porphyrin multilayers

The development of a highly sensitive sensor for oxygen is proposed using a glassy carbon (GC) electrode modified with alternated layers of iron(II) tetrasulfonated phthalocyanine (FeTsPc) and iron(III) tetra-(N-methyl-pyridyl)-porphyrin (FeT4MPyP). The modified electrode showed excellent catalytic activity for the oxygen reduction. The reduction potential of the oxygen was shifted about 330 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare GC electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves 4 electrons with a heterogenous rate constant (k_obs) of 3 × 10⁵ mol⁻¹ L s⁻¹. A linear response range from 0.2 up to 6.4 mg L⁻¹, with a sensitivity of 4.12 μA L mg⁻¹ (or 20.65 μA cm⁻² L mg⁻¹) and a detection limit of 0.06 mg L⁻¹ were obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation (R.S.D.) was 2.0% for 10 measurements of a solution of 6.4 mg L⁻¹ oxygen. The sensor was applied to determine oxygen in pond and tap water samples showing to be a promising tool for this purpose.     

Solvation of excess electrons trapped in charge pockets on hydrated molecular surfaces

We have previously computed a set of hypothetical molecular surfaces, which formed charge pockets that were capable of excess electron entrapment. These charge pockets arose due to the fact that the molecular surfaces possessed an extended network of OH groups on one side of the surface and hydrogen atoms on the opposite side. The uneven distribution of the OH groups coupled to the partial positive charge of the hydrogen atoms caused electrons to be attracted to the surface. In the present investigation we will consider the ability of the hydrogen cyanide (HCN)‐water complex in stabilizing excess electrons on molecular surfaces. The computed vertical detachment energy (VDE) values are high, suggesting anion stability. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Low-symmetry structures of Au32Z (Z = +1, 0, -1) clusters

In this work, we have explored new stable structures of the Au32Z (Z = +1, 0, -1) clusters. Theoretical calculations using density functional theory within the generalized-gradient approximation were performed. Our results show that, in the anion state (Au32-), low-symmetry (disordered) structures are preferred over the caged fullerene-like isomer. In addition, the cationic cluster (Au32+) also exhibits a disordered low-symmetry structure as its lowest energy configuration, but it is much closer in energy to the fullerene-like isomer. These results, obtained at T = 0 K, indicate that disordered structures for the Au32- and Au32+ clusters may be detected not only at room temperature, as was experimentally verified for the Au32- one, but also at much lower temperatures.     

Modeling wave propagation in realistic heart geometries using the phase-field method

We present a novel algorithm for modeling electrical wave propagation in anatomical models of the heart. The algorithm uses a phase-field approach that represents the boundaries between the heart muscle and the surrounding medium as a spatially diffuse interface of finite thickness. The chief advantage of this method is to automatically handle the boundary conditions of the voltage in complex geometries without the need to track the location of these boundaries explicitly. The algorithm is shown to converge accurately in nontrivial test geometries with no-flux (zero normal current) boundary conditions as the width of the diffuse interface becomes small compared to the width of the cardiac action potential wavefront. Moreover, the method is illustrated for anatomically realistic models of isolated rabbit and canine ventricles as well as human atria.     

Boundary critical behavior ofd=2 self-avoiding walks on correlated and uncorrelated vacancies

In this paper we present exact results for the critical exponents of interacting self-avoiding walks with ends at a linear boundary. Effective interactions are mediated by vacancies, correlated and uncorrelated, on the dual lattice. By choosing different boundary conditions, several ordinary and special regimes can be described in terms of clusters geometry and of critical and lowtemperature properties of the model. In particular, the problem of boundary exponents at the -point is fully solved, and implications for-point universality are discussed. The surface crossover exponent at the special transition of noninteracting self-avoiding walks is also interpreted in terms of percolation dimensions.     

Furanyl Alcohols as Alkylating Reagents in Friedel–Crafts Reaction of Arenes

Furanyl alcohols react with arenes by a variant of the Friedel–Crafts reaction to give benzyl furans with fairly satisfying yields. The reaction is mediated by Tf₂O and occurs with reduced times in the presence of Ph₃PO. Some prepared compounds exhibit a lignan‐like backbone.     

Press‐Printed Conductive Carbon Black Nanoparticle Films for Molecular Detection at the Microscale

Carbon black nanoparticle (CBNP) press‐transferred film‐based transducers for the molecular detection at the microscale level were proposed for the first time. Current‐sensing atomic force microscopy (CS‐AFM) revealed that the CBNP films were effectively press‐transferred, retaining their good conductivity. A significant correlation between the morphology and the resistance was observed. The highest resistance was localized at the top of the press‐transferred film protrusions, whereas low values are usually obtained at the deep crevices or grooves. The amount of press‐transferred CBNPs is the key parameter to obtain films with improved conductivity, which is in good agreement with the electrochemical response. In addition, the conductivity of such optimum films was not only Ohmic; in fact, tunneling/hopping contributions were observed, as assessed by CS‐AFM. The CBNP films acted as exclusive electrochemical transducers as evidenced by using two classes of molecules, that is, neurotransmitters and environmental organic contaminants. These results revealed the potential of these CBNP press‐transferred films for providing new options in microfluidics and other related micro‐ and nanochemistry applications.