Reactions of TiCl4, VCl4 and VOCl3 with tetraalkyldiphosphine disulphides

Summary The reactions of MCl₄ (M = Ti or V) with R₂P(S)P(S)R₂ (R = Me or Et) yield hexacoordinate complexes MCl₄ · R₂P(S)P(S)R₂ (M = Ti or V; R = Me or Et), whereas similar reactions with VOCl₃ lead to reduction of vanadium and give rise to the vanadium(IV) pentacoordinated complexes: VOCl₂-R₂P(S)P(S)R₂ (R = Me or Et). All the compounds have been characterized by elemental analyses, i.r., visible and e.p.r. spectra, which show thecis-chelate character of these ligands, although in the complexes containing Et₄P₂S₂ the i.r. spectra indicates that thegauche conformation of the ligand is implicated in bonding to the metal. The occupation of the sixth coordination site in pentacoordinate complexes, VOCl₂ · R₂P(S)P(S)R₂, by different donor solvents, has been studied by means of visible and e.p.r. spectra.     

CO2 adsorption on calcium silicate hydrate gel synthesized by double decomposition method

Journal of Thermal Analysis and Calorimetry - The calcium silicate hydrate gel (C–S–H) was synthesized by the double decomposition method because of the simplicity and the quickness of...     

Effect of the electrodeposition potential on the photoelectroactivity of the SnS/Sb2S3 thin films

Journal of Solid State Electrochemistry - The present work outlines a simple and novel approach to obtain nanostructured and heterostructured SnS/Sb2S3 thin films. This material showed enhanced...     

An inorganic iron complex that inhibits wild-type and an isoniazid-resistant mutant 2-trans-enoyl-ACP (CoA) reductase from Mycobacterium tuberculosis

The in vitro kinetics of inactivation of both wild-type and I21V InhA enzymes by [FeII(CN)5(INH)]3- indicate that this process requires no activation by KatG, and no need for the presence of NADH. This inorganic complex may represent a new class of lead compounds to the development of anti-tubercular agents aiming at inhibition of a validated target.     

Synthesis of 3-substituted 2-cyclohexenones through umpoled functionalization

A new protocol to obtain 3-substituted 2-cyclohexenones, was developed by reversing the chemical reactivity of 2-cyclohexenone. One-pot synthesis of 3-substituted 2-cyclohexenones can be achieved by treatment of 3-phenylthiosilyl enol ether with a mixture of t-BuLi/HMPA that allows hydrogen-selective exchange in presence of reactive electrophiles such as aldehydes, ketones and alkyl halides. This affords the corresponding product in moderate overall yield, after silyl enol ether cleavage and concomitant thiophenol elimination initiated with TBAF.     

Stability of benzoporphyrin photosensitizers in water/ethanol mixtures: pKa determination and self‐aggregation processes

Benzoporphyrin monoacid derivatives, here named B3A and B3B, are promising new drugs for photodynamic therapy. Although both isomers show interesting characteristics as photosensitizing compounds, they have some distinct physicochemical properties such as the tendency to self‐aggregate in water‐rich media. Because pH drives the presence of each species, the pK_a of these compounds assumes strategic importance. However, traditional micro‐titration methods and UV–Vis absorption techniques fail to give reliable pK_a values due to the characteristics of this highly complex system, such as the precipitation of hydrophobic species, close pK_a values, and high absorption band superposition. In the present work, chemometric tools are employed to evaluate pK_a, and the kinetic tendency of monomers to undergo self‐aggregation is investigated. In solvent mixtures at low water percentage in ethanol, both B3A and B3B are stabilized in a monomeric state. However, in mixtures with a high water content, self‐aggregation takes place, mainly under a mild pH acid condition (3 < pH < 6), in which the prevalent protolytic species of both isomers is the neutral charged form, compounds with carboxylic and porphyrin free‐base groups. It is demonstrated that both isomers can undergo aggregation following a self‐catalytic mechanism, which is 2000 times slower to B3A than B3B. For B3A, the aggregation is manifested by a decrease in the monomer band with the aggregation band probably superposed to that of the monomer. For B3B, together with the decrease in the monomer band, a new band related to self‐aggregates is observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Dynamic stability and thermodynamic characterization in an enzymatic reaction at the single molecule level

In this work we study, at the single molecular level, the thermodynamic and dynamic characteristics of an enzymatic reaction comprising a rate limiting step. We investigate how the stability of the enzyme-state stationary probability distribution, the reaction velocity, and its efficiency of energy conversion depend on the system parameters. We employ in this study a recently introduced formalism for performing a multiscale thermodynamic analysis in continuous-time discrete-state stochastic systems.     

Fluctuations of the second order observables for dissipative processes in 19F+27Al system

The excitation function (EF) data for dissipative processes in ¹⁹F + ²⁷Al system in the incident energy interval from 113.5 to 130 MeV are used to obtain the dependence of the charge variance and of the interaction time as a function of the incident energy. Fluctuations are observed in the EFs of both these secondary observables. Their correlation is supported by a mechanism based on stochastic exchange of nucleons.     

On the difficulties of predicting the adsorption of volatile organic compounds at low pressures in microporous solid: the example of ethyl benzene

Adsorption isotherms of toluene and ethyl benzene, at 25 degrees C and 40 degrees C, were determined in two microporous activated carbons and one zeolite. Significant differences were found in the adsorption behavior, at low pressures, between the two vapors on the same adsorbent material. The quantities of adsorbed ethyl benzene at 25 degrees C, in the low-pressure region, were lower than what was observed at 40 degrees C in all the studied adsorbents, contrary to what was found for toluene. This fact was not related to kinetic effects at the two temperatures nor to vapor swelling of the adsorbents structure. Also, there was no molecular sieving since at high pressures the toluene and ethyl benzene occupied the same adsorption space. The differences found in the ethyl benzene adsorption at the two temperatures pose difficulties in the analysis of the adsorption data and, therefore, in the prediction of results. This is discussed in the analysis of the results with the application of the Dubinin-Astakhov equation and in the estimation of the isosteric heats of adsorption. The adsorption potentials of two possible ethyl benzene conformations were estimated for the adsorption in the pores of activated carbon from the Horvath and Kawazoe model, and the values compared with those found experimentally. The results were interpreted in terms of the ethyl benzene conformation effects when the molecule is confined in pores that are about the same size of one of the conformations.