Intramolecular silyl migration in the singlet oxygenation of 2-methyl-5-trimethylsilylfuran

Tetraphenylporphyrin-sensitized photooxygenation of 2-methyl-5-trimethylsilylfuran ($\text{4}$) affords quantitatively trimethylsilyl 2-oxo-4-pentenoate ($\text{5}$), presumably via intramolecular Baeyer-Villiger rearrangement of the intermediary dioxirane ($\text{3a}$).     

Multistep adsorption of anionic dyes on silica/chitosan hybrid. 1. Comparative kinetic data from liquid- and solid-phase models

In this work, a hybrid silica/chitosan was synthesized and characterized by nitrogen elemental analysis and thermal analysis (TG, DTG, DTA, and DSC) and BET surface area. The hybrid was used in adsorption studies of two anionic dyes from aqueous solutions. A rise of temperature accelerates mass transfer of dyes into the hybrid. However, the maximum adsorption capacities reach similar values from 25 to 55 degrees C. The kinetic data were first evaluated in relation to the decrease of the time-related residual concentration of the dyes in solution, where the second-order model has presented the best fitting. The solid-phase interaction of dye data presents a rough fitting to the traditional first-order Lagergren kinetic model. However, a modified Avrami kinetic equation was successfully fitted to the kinetic quantities, where from five to seven kinetic regions were found. A pore-diffusion model has also demonstrated that the diffusion is the rate-controlling interaction mechanism. However, the experimental-calculated comparative values are the best way to evaluate a specific aqueous- or solid-phase kinetic model.     

New designs for inhibitors of the NF-κB: DNA binding

We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-^12,14 -prostaglandin J₂ (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs.     

Evaluation of the calibration errors on cooling of a differential scanning calorimeter using different sets of standard metals

The temperature calibration on cooling of thermal analysis instruments is important for the accurate study of the non-isothermal crystallization kinetics of semi-crystalline polymers. In previous works, a methodology was proposed for performing the calibration on cooling of differential scanning calorimeters (DSCs) with standard metals, and the calibration errors were checked using transitions of high-purity liquid crystals. In this work, alternative, physically meaningful, procedures for carrying out the calibration on cooling are analyzed and validated. The calibration errors are evaluated also with liquid crystalline transitions, when the calibration is performed with standard metals, in a wide temperature range, and when due account is taken for the need of isothermal corrections to the temperature measurements. It is shown that any pair of standard metals may be used to calibrate on cooling, that the calibration errors increase for wider working temperature ranges and that, providing that certain conditions are fulfilled, both calibration procedures yield similar results.     

Computational study of the reaction of N(2D) atoms with CH2F radicals: an example of a barrier-free reaction involving very high internal energies

The singlet potential-energy surface for the N(2D)+CH2F(2A') reaction has been studied employing both second-order M?ller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier. Based on the energy profile for the singlet potential-energy surface, the preferred product should be the most exothermic one, namely, HCN+HF, followed by HNC+HF and FCN+H2. This result seems in contradiction with a computational study of the kinetics of the title reaction in terms of the statistical theories, which leads to the prediction that the production of HNC+HF should be the dominant channel. Consequently, a limited molecular-dynamics study has been carried out, concluding that in fact the system behaves in a nonstatistical way. According to the molecular-dynamics study, the most exothermic channel, HCN+HF, should be the dominant one. An analysis of the possible role of the singlet surface in the reaction of N(4S) with CH2F(2A') has also been carried out. The computational study shows that the microcanonical coefficients for the nonadiabatic channels are much smaller than the competing adiabatic ones. Therefore, the reaction of N(4S) with CH2F(2A') should proceed on the triplet surface without spin change.     

Detection of soil pollution by hydrocarbons using headspace-mass spectrometry and identification of compounds by headspace-fast gas chromatography-mass spectrometry

The direct coupling of a headspace sampler with a mass spectrometer is proposed as a screening tool for the rapid detection of soil pollution by hydrocarbons from petroleum and derivatives. The samples are subjected to the headspace generation process, with no prior treatment, and the volatiles generated are introduced directly into the mass spectrometer, thereby obtaining a fingerprint of the sample analysed. Suitable treatment of the signal by chemometric techniques allows unequivocal characterisation of the different types of sample. The use of fast gas chromatography with a mass spectrometer detector coupled to the headspace sampler allows identification of the major hydrocarbons present in the mineral and organic polluted samples, interpretation of the results obtained, and demonstrates the analytical potential of headspace-mass spectrometry coupling.     

Application of the chemiluminescence systems to evaluate the role of Fcgamma and complement receptors in stimulating the oxidative burst in neutrophils

We have established a luminol- and a lucigenin-dependent CL methods to investigate the role of the receptors for Fc portion of IgG (FcgammaR) and/or complement receptors (CR) in mediating the oxidative burst in neutrophils from systemic lupus erythematosus (SLE) patients compared with healthy controls. In the luminol-CL system, all the reactive oxygen species (ROS) are responsible for light production, whereas in the lucigenin-CL system, only the first ROS generated, converts the lucigenin into an unstable intermediate molecule, which also emits light. First, neutrophils from healthy controls and SLE patients were stimulated with different IC opsonized or not with complement from normal human serum (NHS) or SLE serum, in presence of 10(-4) M luminol. This method was able to differentiate the role of the FcgammaR, CR and FcgammaR/CR co-operation in mediating the oxidative burst, as well as show that the oxidative burst mediated by these receptors was reduced in neutrophils from SLE patients. Second, neutrophils from healthy controls and SLE patients were stimulated with different IC, opsonized or not with NHS, in presence of 10(-3) M lucigenin. In this case, the lucigenin-CL system was also able to differentiate the role of FcgammaR and FcgammaR/CR co-operation, as well as show differences among healthy controls and two different groups of SLE patients according to their clinical manifestations. In conclusion, we have established two sensitive CL systems to study the role of FcgammaR and/or CR in stimulating the oxidative burst of neutrophils, which can be applied in monitoring the involvement of these receptors in the immunopathogenesis of SLE.     

Novel synthesis of sterically hindered N-substituted lactams from imides

An efficient and practical synthesis of sterically hindered N-substituted lactams has been developed starting from simple starting materials. The stereochemistry of the synthetically useful N,N acetal intermediate has been established.     

Kinetics and Mechanism of Ni(II) Chelation in Model and Real Solutions of Xylem Sap of Quercus ilex

The kinetics of formation and dissociation of Ni(II) complexes with oxalic and citric acids was studied by cyclic voltammetry in model solutions of xylem sap of Q. ilex (the dominant tree growing on serpentine soils of Northeast Portugal) using representative concentrations, pH and ionic strength. The role of magnesium on complex formation was analyzed from solutions where Mg is present at concentration levels found in the xylem sap of Q. ilex growing on both nonserpentine and serpentine soils. Kinetics studies were also done in diluted solutions of real xylem sap samples, spiked with increasing amounts of magnesium. The values obtained for the apparent rate constants were those anticipated by the proposed model. To test the validity of the methodology and mechanisms, formation rate constants, k_f (M^?1 s^?1) of Ni(II) complexes with citrate and oxalate were evaluated that compare with the values from Eigen mechanism.     

Dynamical structure of linearizedGL(4) gravities

The physical content of the three more natural models ofGL(4) gravity is analyzed, for the case of weak fields. The first model we deal with is the linearized version of Yang's onetensor-field gravity. It is shown that this is a scalar-tensor theory, with its scalar part contained in the symmetric tensorh , instead of appearing explicitly, externally to the symmetric tensorh , as happens in Brans-Dicke type of scalar-tensor theories. The second and the third linearized models, which can both be derived from the fourth-order action postulated by Yang, turn out to be two-tensor decoupled systems. In both cases one of the tensors is the symmetric weak metric gravity tensor field. The second tensor appearing in these two models, representing theGL(4)-gauge field, is either a linearized symmetric affinity (in the second model) or a linearized but nonsymmetric affinity (for the third model). It is shown that in these last two cases the affinity contains a helicity-3 propagating field. The connection is also given between the fourth-order system which determines the dynamical structure (for the last two models) of the metric tensor and the third-order Yang model of gravity. Owing to the presence of helicity-3 fields we show that it is better to regard Yang's action as an action for a two-tensor system instead of trying to recover from it a pure gravity (one-tensor-field) action. Finally, it is shown what is the dynamical structure of the second and third linearized two-tensor models which can be derived from Yang's action.On leave of absence from the Universidad Simón Bolívar.