Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

Study of the pore size distribution and fractal dimension of HNO3-treated activated carbons

In the present work, the effect of the oxidizing treatment with nitric acid on three activated carbon samples has been studied. The influence of the acid treatment on the surface groups of the different samples has been investigated by means of FT-IR spectroscopy. The pore size distributions of the different samples were determined by means of the HK and DFT methods. The HK method points out a moderate increment of the microporosity due to the action of the nitric acid, whereas the DFT method shows an increase in the microporosity range above 17 Å. Finally, the values of the fractal dimension reveal that the treatment of the samples with nitric acid leads to chemical reactions of a limited extent.     

Algebraic Formulation of Quantum Decoherence

An algebraic formalism for quantum decoherence in systems with continuous evolution spectrum is introduced. A certain subalgebra, dense in the characteristic algebra of the system, is defined in such a way that Riemann–Lebesgue theorem can be used to explain decoherence in a well defined final pointer basis.     

Supersymmetry and bosonization in three dimensions

We discuss on the possible existence of a supersymmetric invariance in purely fermionic planar systems and its relation to the fermion-boson mapping in three-dimensional quantum field theory. We consider, as a very simple example, the bosonization of free massive fermions and show that, under certain conditions on the masses, this model displays a supersymmetric-like invariance in the low energy regime. We construct the purely fermionic expression for the supercurrent and the non-linear supersymmetry transformation laws. We argue that the supersymmetry is absent in the limit of massless fermions where the bosonized theory is non-local.     

A SAXS study of the nanostructural characteristics of TEOS-derived sonogels upon heat treatment up to 1100 °C

Xerogels obtained from the acid-catalyzed and ultrasound stimulated hydrolysis of TEOS were submitted to heat treatment at temperatures ranging from 60 to 1100 °C and studied by small-angle X-ray scattering (SAXS). The SAXS intensity as a function of the modulus of the scattering vector q was obtained in the range from q₀=0.19 to q_m=4.4 nm⁻¹. At 60 °C the xerogels exhibit an apparent surface fractal structure with a fractal dimension D_S∼2.5 in a length scale ranging from 1/q₁∼1 to 1/q_m∼0.22 nm. This structure becomes extremely rough at 120 °C (D_S∼3) and at 150 °C, it apparently converts to a mass fractal with a fractal dimension D∼2.4. This may mean an emptying of the pores with preservation of a share of the original mass fractal structure of the wet aged gel, for it had presented a mass fractal dimension D∼2.2. A well characterized porous structure formed by 2.0 nm mean size pores with smooth surface of about 380 m²/g is formed at 300 °C and remains stable until approximately 800 °C. At 900 °C the SAXS intensity vanishes indicating the disappearance of the pores in the probed length scale. The elimination of the nanopores occurs by a mechanism in which the number of pores diminishes keeping constant their mean size. The xerogels exhibit a foaming phenomenon above 900 °C and scatter following Porod's law as does a surface formed by a coarse structure.     

Preparation and characterization of activated carbons from impregnation pitch by ZnCl2

Using an impregnation pitch from bituminous coal tar (OP) supplied by Industrias Químicas del Nalon Company as raw material, two phases (isotropic and anisotropic) have been obtained. The latter was used as precursor for the preparation of activated carbons. First, a chemical activation process was carried out with ZnCl₂ as activating agent. The process was conducted at different concentrations and temperatures and by means of impregnation with solid zinc chloride. Optimal values were obtained for samples prepared by using a ZnCl₂:pitch ratio equal to 3:1 (sample AZn3). Next, this sample was thermally treated at two different temperatures, i.e., 700 and 800 °C. A lose of specific surface area, microporosity and mesoporosity was observed with respect to sample AZn3, such a lose being more remarkable as temperature increased. Moreover, impregnation of the anisotropic phase of the original pitch with an aqueous solution of ZnCl₂ followed by thermal treatment resulted in a poorly developed surface area and porous texture, probably due to the presence of Zn complexes, which interfere with the activation process.     

New extraction method for the analysis of linear alkylbenzene sulfonates in marine organisms. Pressurized liquid extraction versus Soxhlet extraction

A new method has been developed for the determination of linear alkylbenzene sulfonates (LAS) from various marine organisms, and compared with Soxhlet extraction. The technique applied includes the use of pressurized liquid extraction (PLE) for the extraction stage, preconcentration of the samples, purification by solid-phase extraction (SPE) and analysis by liquid chromatography with fluorescence detection. The spiked concentrations were added to the samples (wet mass of the organisms: Solea senegalensis and Ruditapes semidecussatus), which were homogenized and agitated continuously for 25 h. The samples were extracted by pressurized hot solvent extraction using two different extraction temperatures (100 and 150 degrees C) and by traditional Soxhlet extraction. The best recoveries were obtained employing pressurized hot solvent extraction at 100 degrees C and varied in the range from 66.1 to 101.3% with a standard deviation of between 2 and 13. Detection limit was between 5 and 15 microg kg(-1) wet mass using HPLC-fluorescence detection. The analytical method developed in this paper has been applied for LAS determination in samples from a Flow-through exposure system with the objective of measuring the bioconcentration of this surfactant.     

Multivariate calibration of near infrared spectra by orthogonal WAVElet correction using a genetic algorithm

Orthogonal WAVElet correction (OWAVEC) is a pre-processing method aimed at simultaneously accomplishing two essential needs in multivariate calibration, signal correction and data compression, by combining the application of an orthogonal signal correction algorithm to remove information unrelated to a certain response with the great potential that wavelet analysis has shown for signal processing. In the previous version of the OWAVEC method, once the wavelet coefficients matrix had been computed from NIR spectra and deflated from irrelevant information in the orthogonalization step, effective data compression was achieved by selecting those largest correlation/variance wavelet coefficients serving as the basis for the development of a reliable regression model. This paper presents an evolution of the OWAVEC method, maintaining the first two stages in its application procedure (wavelet signal decomposition and direct orthogonalization) intact but incorporating genetic algorithms as a wavelet coefficients selection method to perform data compression and to improve the quality of the regression models developed later. Several specific applications dealing with diverse NIR regression problems are analyzed to evaluate the actual performance of the new OWAVEC method. Results provided by OWAVEC are also compared with those obtained with original data and with other orthogonal signal correction methods.