RESUMO
CH stretching bands, nu(CH), in the infrared spectrum of single crystals of nominally high purity, of laboratory-grown MgO, and of natural upper mantle olivine, provide an "organic" signature that closely resembles the symmetrical and asymmetrical C--H stretching modes of aliphatic -CH(2) units. The nu(CH) bands indicate that H(2)O and CO(2), dissolved in the matrix of these minerals, converted to form H(2) and chemically reduced C, which in turn formed C--H entities, probably through segregation into defects such as dislocations. Heating causes the C--H bonds to pyrolyze and the nu(CH) bands to disappear, but annealing at 70 degrees C causes them to reappear within a few days or weeks. Modeling dislocations in MgO suggests that the segregation of C can lead to C(x) chains, x = 4, with the terminal C atoms anchored to the MgO matrix by bonding to two O(-). Allowing H(2) to react with such C(x) chains leads to [O(2)C(CH(2))(2)CO(2)] or similar precipitates. It is suggested that such C(x)--H(y)--O(z) entities represent protomolecules from which derive the short-chain carboxylic and dicarboxylic and the medium-chain fatty acids that have been solvent-extracted from crushed MgO and olivine single crystals, respectively. Thus, it appears that the hard, dense matrix of igneous minerals represents a medium in which protomolecular units can be assembled. During weathering of rocks, the protomolecular units turn into complex organic molecules. These processes may have provided stereochemically constrained organics to the early Earth that were crucial to the emergence of life.
RESUMO
A flow injection analysis method is described to determine fluticasone propionate, based upon a novel adaptation of the reaction of o-phthalaldehyde with a thiol and a primary amine. The method, which allows both UV and fluorescence detection, has been optimised using experimental design. First a screening is executed to select the significant factors and in a second step these factors are optimised with the variable-size simplex algorithm. In the screening step, a two-level fractional factorial design is compared with an asymmetrical design containing the same number of experiments, but in which one factor is at three levels. It was found that in both designs the same significant variables are detected for the two-level factors, but that for the three-level factor the asymmetrical design confirms an expectation of having a (local) optimum in the examined domain, whilst from the two-level design this is not at all apparent. Complete optimisation was carried out for both UV and fluorescence detection. The two detection methods did not have the same significant variables. For the UV detection, the temperature and the pH adjustment on-line (concentration of sodium hydroxide and amount of boric acid) were the most critical parameters. For the fluorimetric detection the temperature and the fraction of methanol were critical. Moreover the conditions found to be optimal are different for both detection methods.