Formation of simple organic molecules in the interstellar medium

In this work we present a methodology for the synthesis of simple molecules from basic formaldehyde (H₂CO) precursors. We have approached this challenging problem by considering a basic dimerization scheme that eventually leads to diose and methyl formate, using an HCO⁺ proton source. This species was chosen due to its ample abundance in the atmosphere. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

The electronic origin of unusually large nJFN coupling constants in some fluoroximes

SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through‐space transmission of J_FN coupling constants for the fluoroximes studied in this work. Because of the well‐known behavior of FC term, a new rationalization for the experimental ^TSJ_FN SSCC is presented. It is mainly based on the overlap matrix (S_ij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (D_ij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non‐bonding electron pairs involved in D_ij. In using this approach, a linear correlation between ^TSJ_FN versus D_ij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so‐called through‐space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through‐space coupling, it should better be dubbed as ‘through overlapping orbital coupling’. Copyright © 2013 John Wiley & Sons, Ltd.     

Exploring the structural and electronic properties of nitrogen-containing exohydrogenated carbon nanotubes: a quantum chemistry study

Saturated nanotubes consisting of 2–10 and 20 layers of cyclic units of six-membered rings, each one having a pyrimidine-like framework (i.e., –C–C–C–N–C–N–), were studied by quantum chemistry methods using Density Functional Theory (DFT) at the B3LYP/6-31G* level of theory. Four different nanotube (NT) configurations were theoretically studied in this work. They were formed by covalently arranging each layer over the other, with uniform relative rotations of 0°, 60°, 120°, and 180° with respect to each of the layers. Different structures can be created by modulating the relative rotation as layers are added to the main nanostructure. NTs with a relative rotation of 60° showed both greater stabilities and highest potential for catalytic activity. All of them showed band gaps of around 0.2 eV. Charges and other properties can be controlled by appropriate layer arrangement. The studied families of NTs have a very small diameter and could find potential applications in chemistry, physics, and medicine.     

The hausdorff dimension of the harmonic class on negatively curved surfaces

We study the regularity of the Hausdorff dimension of the harmonic class of a surface M of negative curvature as a function of the riemannian metric. We prove that it is a C^{r− 3} function of the metric in the Banach manifold of C^r riemannian metrics on M. We also prove regularity results for some asymptotic quantities associated to the Brownian motion on M.     

Temperature spectra from a turbulent thermal plume by ultrasound scattering

This paper reports the results of a study on temperature inhomogeneities conducted on a thermal plume by using ultrasound scattering as a non-intrusive measurement technique. The plume rises from a metallic disk which can be heated up to 800 °C. The working fluid is air at atmospheric pressure. In the measurement technique, an incoming ultrasound wave is emitted towards the thermal plume. The incident wave is scattered because of non-linear couplings with the flow instabilities present in the measurement region. The scattered wave carries information about those flow instabilities. The technique allows for the retrieving of this information. The shape of the obtained spectrum of temperature fluctuations as a function of wave vector modulus is consistent with previous theoretical analysis. Three qualitatively different regions were identified: first, a production region characterized by a q² law; secondly, a region with behavior as per q⁻³ associated with a buoyancy region and; finally, a dissipation region associated with a q⁻⁷ law. These spectral regions characterize the energy transfers mechanisms among the length scales of flow investigated here. A coefficient of anisotropy γ was defined to analyze anisotropic features of the flow.     

Stereochemical dependence of 3JCH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives

Theoretical and experimental studies on (3)J(C2H6eq) NMR spin-spin coupling constants in both the 2-X-4-t-butyl-cyclohexanone (X = H, CH(3), F, Cl, and Br) and in their alcohol derivatives series are reported. Results thus found are rationalized in terms of the transmission of the Fermi contact contribution to such couplings. To this end, dependencies of (3)J(C2H6eq) couplings versus the C(2)-C(1)-C(6) angle are compared in both series for equatorial and axial X orientations. The main trend is described in terms of the rear lobes interaction. Besides, for X = halogen atom in equatorial orientation a rather strong interaction between oxygen and halogen lone pairs is observed, and its influence on (3)J(C2H6eq) couplings is discussed and rationalized in terms of different Fermi contact transmission pathways.     

Acid natural clinoptilolite: structural properties against adsorption/separation of n-paraffins

The employment of an acid natural clinoptilolite (AZH-1) in the adsorption and separation of n-paraffins has been evaluated. Natural clinoptilolite, NZ, was the raw material used to prepare the sodium-exchanged clinoptilolite (AZ) starting from which the AZH-1 sample was obtained by acid treatment. The structural stability of the samples after the applied treatments was demonstrated. The nitrogen adsorption experiments indicated that the acid sample has a homogeneous porous distribution and a considerable increase in the micropore volume with respect to NZ and AZ. The employment of the inverse gas chromatography at infinite dilution (IGCID) allowed studying the adsorption and separation of n-paraffin mixtures on AZH-1. It was also confirmed that the diffusion on AZH-1 took place in an unblocked structure through the A channel of ten members with minimal interactions. The IGCID results demonstrated the capacities of the acid Cuban natural zeolite in the adsorption and separation of n-paraffin mixtures.     

Analysis of Plant–Plant Interactions Reveals the Presence of Potent Antileukemic Compounds

A method to identify anticancer compounds in plants was proposed based on the hypothesis that these compounds are primarily present in plants to provide them with an ecological advantage over neighboring plants and other competitors. According to this view, identifying plants that contain compounds that inhibit or interfere with the development of other plant species may facilitate the discovery of novel anticancer agents. The method was developed and tested using Magnolia grandiflora, Gynoxys verrucosa, Picradeniopsis oppositifolia, and Hedyosmum racemosum, which are plant species known to possess compounds with cytotoxic activities. Plant extracts were screened for growth inhibitory activity, and then a thin-layer chromatography bioautography assay was conducted. This located the major antileukemic compounds 1, 2, 4, and 5 in the extracts. Once the active compounds were located, they were extracted and purified, and their structures were determined. The growth inhibitory activity of the purified compounds showed a significant correlation with their antileukemic activity. The proposed approach is rapid, inexpensive, and can easily be implemented in areas of the world with high biodiversity but with less access to advanced facilities and biological assays.