Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.     

Titanium Dioxide/Electrolyte Solution Interface: Electron Transfer Phenomena

Electron transfer between a titanium dioxide/electrolyte solution interface has been studied. As found by other researchers of similar interfaces (TiO(2)- and ZnO-electrolyte solution), a slow consumption of OH(-) ions takes place in this type of interface. A theoretical model has been developed for calculating the change in the Fermi energy of both electrolyte solution and semiconductor, showing that ion consumption from the solution is favoured by the decrease of the difference between their Fermi energies. A kinetic constant (upsilon) is found to characterise the consumption process, its value increasing with electrolyte and semiconductor mass concentrations. Furthermore, this process may be used to estimate the point of zero charge of a titanium dioxide colloidal dispersion. Copyright 2000 Academic Press.     

High-performance liquid chromatographic screening of chlorophyll derivatives produced during fruit storage

Reversed-phase high-performance liquid chromatography with photodiode array and fluorescence detection was applied to the systematic screening of chlorophylls and derivative pigments. The chromatographic procedure proposed made it possible to successfully separate and identify eight chlorophyll derivatives (the a and b forms of chlorophyll, chlorophyllide, pheophytin and pheophorbide) by using a linear gradient of methanol, acetone and ammonium acetate. The method has been routinely applied to study chlorophyll degradation during the postharvest storage of cherimoya (Annona cherimola, Mill.) fruits. The brilliant green colour even at maturity, and its high chlorophyllase and Mg-dechelating activities, indicate that this plant material might be suitable for investigating the as yet not well known chlorophyll breakdown processes.     

Thermal characterization of antimicrobial drug ornidazole and its compatibility in a solid pharmaceutical product

The ornidazole drug substance presents melt at approximately 90 °C (∆T = 85–98 °C), which is critical for its use on pharmaceutical manufacturing process. This work aimed the thermal characterization of ornidazole raw-material synthesized by three different manufacturers from India, China, and Italy, using the thermoanalytical techniques of DTA, DSC, and TG, besides the verification of its stability and compatibility as a solid pharmaceutical product by the analysis of its binary mixtures (BM) with excipients and a tablet formulation. The characterization includes the thermal decomposition kinetic investigation by Ozawa model using Arrhenius equation and drug purity determination by Van’t Hoff equation. The DSC purity determination and precision were compared with results from UV–Vis spectrophotometric and liquid chromatography, showing an adequate correlation before being recommended as a general method for purity assay. The drug raw-materials presented similar quality and zero-order kinetic behavior, besides showing differences on thermal stability. The drug presented compatibility with the tested excipients since the BM studied presented melting at the same temperature range as the drug and a decomposition temperature similar to the drug for two of the BM, and at a higher temperature for the others three of the BM evaluated, which presented excipients with higher molecular structure, capable of spatial coating on the small drug molecule promoting a physical interaction pharmaceutical acceptable. The tablet was processed by wet granulation and compressed under normal conditions of pressure and temperature, maintaining the physical properties of solid drug approving the manufacturing process used. In this study, the thermal analysis was used with success as an alternative method to characterize, quantify, and perform a preformulation study.     

Multiple Decay Mechanisms and 2D‐UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine‐Uracil Monophosphate

The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D‐UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine ¹L_a state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine ¹L_b and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter‐base hydrogen transfer and decay to the ground state through a conical intersection, or it can yield a long‐lived minimum stabilized by a hydrogen bond between the two ribose rings. This suggests that the ¹L_b, S(U) and CT states of the stacked conformer may all contribute to the experimental lifetimes of 18 and 240 ps. We have also simulated the time evolution of the 2D‐UV spectra and provide the specific fingerprint of each species in a recommended probe window between 25 000 and 38 000 cm^?1 in which decongested, clearly distinguishable spectra can be obtained. This is expected to allow the mechanistic scenarios to be discerned in the near future with the help of the corresponding experiments. Our results reveal the complexity of the photophysics of the relatively small ApU system, and the potential of 2D‐UV spectroscopy to disentangle the photophysics of multichromophoric systems.     

Active bogies and chassis levelling for a vehicle operating in rough terrain

Four axle vehicles with bogies can adapt the position of the wheels to follow irregularities in the terrain, having an obstacle surpassing ability far greater than conventional 2-axle vehicles. Still, the ability to overcome discrete obstacles on a steep slope is very different depending on the wheel that is facing the obstacle. A possible solution to diminish this variation can be found if the vehicle is able to actively redistribute the load on each wheel. One strategy is to design the suspension mechanism so it can regulate its height, being able to level the chassis. Also, an active torque on the pin join between the bogie and the chassis can be applied with the same goal, adopting a system of active bogies. Both solutions have been parametrically studied in a bi-dimensional multibody model of a 4-axle vehicle with double bogies. The results show an improvement independent of obstacle position and terrain angle when using active bogies. With height regulation, this improvement is limited to the rear bogie wheels, but the obstacle surmounting capacity of the vehicle as a whole can be considerably increased if the optimal regulation point is found. Possible applications for such enhanced vehicles with bogies are performing different tasks in forest areas with obstacles on steep slopes or unstructured terrain exploration.     

Sequential N-acylamide methylenation-enamide ring-closing metathesis: construction of benzo-fused nitrogen heterocycles

The dimethyltitanocene methylenation of N-acylamides derived from ortho-vinylanilines, ortho-allylaniline, and ortho-vinylbenzylamine provides the corresponding enamides, which upon exposure to the second generation Grubbs ruthenium catalyst give access to indoles, 1,4-dihydroquinolines, and 1,2-dihydroisoquinolines, respectively. This sequential protocol also allows the synthesis of dihydrobenzoazepines, although the ring-closing metathesis (RCM) step is complicated by the alkene isomerization processes. From certain substrates, the direct annulation is observed in the titanium-mediated step, which is likely to occur through an olefin metathesis-intramolecular olefination sequence.     

Pseudoscalar meson masses in unitarized chiral perturbation theory

This contribution summarizes the work explained in arXiv:hep-ph/0608290 where we perform a non-perturbative chiral study of the masses of the lightest pseudoscalar mesons. The pseudoscalar self-energies are calculated by the evaluation of the scalar self-energy loops with full S-wave meson-meson amplitudes taken from Unitary Chiral Perturbation Theory (UCHPT). These amplitudes, among other features, contain the lightest nonet of scalar resonances σ, f ₀(980), a ₀(980) and κ. The self-energy loops are regularized by a proper subtraction of the infinities within a dispersion relation formulation of the amplitudes. Values for the bare masses of pions and kaons and the η ₈ mass are obtained. We then match to the self-energies from standard Chiral Perturbation Theory (CHPT) to O(p ⁴) and resum higher orders from our calculated scalar self-energies. The dependence of the self-energies on the quark masses allows a determination of the ratio of the strange-quark mass over the mean of the lightest-quark masses, m _s/ , in terms of the O(p ⁴) CHPT low-energy constant combinations 2L ^r ₈ - L ^r ₅ and 2L ^r ₆ - L ^r ₄. In this way, we give a range for the values of these low-energy counterterms and for 3L ₇ + L ^r ₈, once the η-meson mass is invoked. The low-energy constants are further constraint by performing a fit to the recent MILC lattice data on the pseudoscalar masses, and m _s/ = 25.6±2.5 results. This value is consistent with 24.4±1.5 from CHPT and phenomenology and more marginally with the value 27.4±0.5 obtained from pure perturbative chiral extrapolations of the MILC lattice data to physical values of the lightest-quark masses.