Theoretical study of ribonucleotide reductase mechanism-based inhibition by 2'-azido-2'-deoxyribonucleoside 5'-diphosphates

2'-azido-2'-deoxyribonucleoside 5'-diphosphates are mechanism-based inhibitors of Ribonucleotide Reductase. Considerable effort has been made to elucidate their mechanism of inhibition, which is still controversial and not fully understood. Previous studies have detected the formation of a radical intermediate when the inhibitors interact with the enzyme, and several authors have proposed possible structures for this radical. We have conducted a theoretical study of the possible reactions involved, which allowed us to identify the structure of the new radical among the several proposals. A new reactional path is also proposed that is the most kinetically favored to yield this radical and ultimately inactivate the enzyme. The energetic involved in this mechanism, both for radical formation and radical decay, as well as the calculated Hyperfine Coupling Constants for the radical intermediate, are in agreement with the correspondent experimental values. This mechanistic alternative is fully coherent with remaining experimental data.     

Synthesis of non-agglomerated Ba<Subscript>0.77</Subscript>Ca<Subscript>0.23</Subscript>TiO<Subscript>3</Subscript> nanopowders by a modified polymeric precursor method

In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba_0.77Ca_0.23TiO₃ nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis, morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy. In summary, Ba_0.77Ca_0.23TiO₃ nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution (30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the chelation in higher pHs.     

Principal component analysis of the effects of wavefunction modification on the electrostatic potential of indole

The molecular electrostatic potential (MEP) of the indole molecule was calculated in a three‐dimensional grid in which the molecule was centered at the origin. To evaluate the dependence of MEP on the type of calculation, semiempirical, ab initio, and density functional theory methods with different basis sets were employed. The data matrix generated by these calculations was analyzed by principal component analysis (PCA). The appearance of outliers and the effect of wavefunction modifications such as the introduction of electron correlations and diffuse functions were highlighted by the use of PCA. The spatial localization of such effects around the molecule was possible from the loadings values associated with the graphical analysis of the grid points. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants

Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results.     

The site of protonation of bifunctional bases with competing basic centers. I. Aromatic nitriles

The experimental values of the gas-phase proton affinities for a variety of 4-substituted benzonitriles, 4-substitutedN, N-dimethylanilines, and 4-substituted benzaldehydes have been examined by means of correlation analysis techniques and by ab initio quantum mechanical methods (MP2/ 6-31G(d) level). From this study it is concluded that in the gas phase, 4-(dimethylamino)-benzonitrile essentially protonates on the dimethylamino group, while protonated 4-cyanobenzaldehyde is very nearly a 21 mixture of the carbonyl- and cyano-protonated forms.This work is dedicatedin memoriam to Professor Robert W. Taft.     

Prediction of adsorption of organic component and water vapour mixture onto activated carbon

A simple isotherm equation is derived for the adsorption of an organic component onto activated carbon in presence of water vapour. The theoretical results are compared with experimental data for toluene-water vapour-activated carbon, which were published byRipperger andGermerdonk [10].

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Vorhersage der Adsorption einer organischen Komponente und Wasserdampf an Aktivkohle

Zusammenfassung Es wird eine einfache Adsorptionsisotherme abgeleitet, welche die gleichzeitige Adsorption eines organischen Stoffes und Wasser an Aktivkohle beschreibt. Die theoretischen Ergebnisse werden mit experimentellen Resultaten vonRipperger undGermerdonk [10] für Toluol-Wasser-Aktivkohle verglichen.

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Symbols a _i adsorbate concentration in adsorbent, kg/kg of carbon - a _0i monolayer capacity, kg/kg of carbon - b _i kinetic parameter of theLangmuir equation - E _j adsorption energy in thej-th layer - i i-th component (1 — water vapour, 2 — organic compound) - j j-th layer - m number of layers - n number of adsorbed components - p partial pressure, Pa - p* saturation partial pressure, Pa - p _C water vapour partial pressure at begining of capillary condensation, Pa - surface coverage     

Evaluation of isothermal kinetic of sweetener

Summary Sulfonylureas are widely used for the treatment of non-insulin dependent diabetes mellitus. Glibenclamide belongs to the group of substituted arylsulfonylureas. Many representative of this group shows polymorphism. The purpose of this work was to investigate the thermal behaviour and compatibility between glibenclamide and some excipients using thermoanalytical techniques (TG-DTG/DSC). The thermal and isothermal kinetics data showed incompatibility between glibenclamide and magnesium stearate.     

Phase equilibria in the ternary system PbO−P2O5−PbCl2

Journal of Thermal Analysis and Calorimetry - In the ternary system PbO?P2O5?PbCl2, the partial ternary system Pb5Cl2O4?Pb3Cl2O2?Pb10(PO4)6Cl2 was examined by thermal,...     

Fluorescence quenching of anthropogenic fulvic acids by Cu(II), Fe(III) and UO(2)(2+)

The quenching of the fluorescence of three anthropogenic fulvic acids (FA) provoked by Cu(II) (pH 6.0), Fe(III) (pH 4.0) and UO₂²⁺ (pH 3.5), was analyzed by a non-linear method and by Stern-Volmer plots. The FA samples were extracted from composted sewage sludges (csFA), composted municipal wastes (mwFA) and composted livestock wastes (lsFA). Synchronous-scan fluorescence (SyF) spectra were collected as a function of metal ion concentration. Spectral data were treated by a self-modeling mixture analysis method (SIMPLISMA) to detect the SyF spectral band with the strongest quenching and to calculate the corresponding quenching profile. The analysis of these profiles by a non-linear method allowed the estimation of conditional stability constants (K) and of the percentage of non-complexing fluorophores. The same quantitative information was obtained by the modified Stern-Volmer equation taking into account the existence of fluorophores that do not participate in the complexation. Good agreement was found between the results of the two procedures. The log K calculated by the non-linear method were (standard deviation in parenthesis): csFA, Cu(II), 4.22 (5); Fe(III), 5.0 (1); UO₂²⁺, 5.2 (2); mwFA, Cu(II), 4.21 (3); Fe(III), 5.6 (2); UO₂²⁺, 4.7 (3); lsFA, Cu(II), 4.51 (8); Fe(III), 5.5 (2); UO₂²⁺, 3.6 (2).     

Molecular Imprinting in Sol-Gel Materials: Recent Developments and Applications

Since its inception five decades ago, imprinted sol-gel materials went practically unnoticed, until in the 1970s the conceptual introduction of molecular imprinting in synthetic polymers triggered a new interest in this field. The recent growth in interest in organic–inorganic hybrid materials prepared by sol-gel chemistry and the development of a variety of new strategies for imprinting polymeric matrices have led to a growing activity in what became known as molecularly imprinted sol-gel materials. This paper intends to give an overview of recent progress in molecular imprinting in sol-gel matrices, the potential analytical applications of these tailor-made materials and their limitations, with the aim of drawing attention to useful information and to enhancing interest in this practically unexplored but promising field.