DFT study on the complexation of anions with 1,4,7,10,13,16-hexaazacyclooctodeca-2,5,8,11,14,17-hexaene

Macrocyclic compounds have been widely used as anion carriers, as they play important functions in chemical and biological systems. This work reports a theoretical study on free 1,4,7,10,13,16-hexaazacyclooctodeca-2,5,8,11,14,17-hexaene (HAC), as well as its complex with fluoride, chloride, bromide and acetate anions, with and without the presence of the sodium counterion, in the gas phase and implicit solvents (cyclohexane and acetonitrile), at the ωB97X-D/6-311G(d,p) level. The negative ?G⁰ values indicate that the crown-anion complex is prone to be formed due to hydrogen bonds in all tested media. Nevertheless, such interactions weaken as the solvent polarity increases. The ΔG⁰ _C6H12 values decrease when the counterion is taken into account, reinforcing the formation of the Na⁺?HAC?X^? complex. However, the complexation is disfavored in polar solution, since the presence of the counterion increases the HAC-anion distance. Natural bond orbital analysis, the quantum theory of atoms in molecules and non-covalent interactions methods explored the nature and strength of the hydrogen bond interactions, while spin–spin coupling constant calculations for the fluoride-based complex (^1h J _F,H(N)) gave insight into the potential of this NMR parameter to experimentally probe the complexation of HAC with fluoride.     

Long-term evolution of mid-altitude quasi-satellite orbits

Quasi-satellite orbits are of great interest for the exploration of planetary moons because of their dynamical features and close proximity with respect to the surface of scientifically relevant objects like Phobos and Deimos. This paper explores the equations of the elliptical Hill problem, offering a new analytical insight into the long-term evolution of mid-altitude quasi-satellite orbits. Our developments are based on the Yamanaka–Ankersen solution of the Tschauner–Hempel equations and capture the effects of the secondary’s gravity and orbital eccentricity on the shape and orientation of near-equatorial retrograde relative trajectories. The analytical solution of the in-plane and out-of-plane components of the secular motion is achieved by averaging over the relative longitude of a spacecraft as seen from the co-rotating frame of the two primaries. Developments are validated against the numerical integration of quasi-periodic trajectories that densely cover the surface of three-dimensional invariant tori. This analysis confirms the stable nature of quasi-satellite orbits and provides new tools for future spacecraft missions such as the Martian Moons eXploration envisaged by JAXA.

     

An anomalous effect of fluorine on the conformational equilibrium of 2-fluorocyclohexane-1,3-dione

Conformational stabilities of 2-halocyclohexane-1,3-diones are strongly affected by steric and dipolar effects involving the carbonyl groups and the equatorial halogen. However, 2-fluorocyclohexane-1,3-dione has been found to be mostly equatorial, because of electron delocalization in this conformer that overcomes repulsive interactions, while the other halogen derivatives perform as expected.     

Electrochemical detection of 2,4,6-trinitrotoluene on carbon nanotube modified electrode: Effect of acid functionalization

Journal of Solid State Electrochemistry - This work presents new insights on the electrocatalytic reduction of 2,4,6-trinitrotoluene (TNT) on carbon nanotubes (CNTs)-modified electrodes...     

Theoretical and infrared studies on the conformational isomerism of trans-2-bromo-alkoxycyclohexanes

The infrared spectra of trans-2-bromo-alkoxycyclohexanes (alcoxy = OMe, OEt, O(i)Pr and O(t)Bu) were obtained for the neat liquid, and the C-Br stretching mode was quantitatively analyzed to give insight about the conformational isomerism of these compounds. Frequency calculations supported the band assignments, and the relative band intensities suggest that the diaxial conformer is prevalent for the methoxy and tert-butoxy derivatives (51 and 56%, respectively), while the diequatorial form is preponderant for the ethoxy and isopropoxy derivatives (76 and 77%, respectively). Therefore, the size of the alkoxy group plays a determinant role in determining the conformational preferences of the title compounds.     

Low-energy electron collisions with glycine

We report cross sections for elastic electron scattering by gas phase glycine (neutral form), obtained with the Schwinger multichannel method. The present results are the first obtained with a new implementation that combines parallelization with OpenMP directives and pseudopotentials. The position of the well known π* shape resonance ranged from 2.3 eV to 2.8 eV depending on the polarization model and conformer. For the most stable isomer, the present result (2.4 eV) is in fair agreement with electron transmission spectroscopy assignments (1.93 ± 0.05 eV) and available calculations. Our results also point out a shape resonance around 9.5 eV in the A' symmetry that would be weakly coupled to vibrations of the hydroxyl group. Since electron attachment to a broad and lower lying σ* orbital located on the OH bond has been suggested the underlying mechanism leading to dissociative electron attachment at low energies, we sought for a shape resonance around ~4 eV. Though we obtained cross sections with the target molecule at the equilibrium geometry and with stretched OH bond lengths, least-squares fits to the calculated eigenphase sums did not point out signatures of this anion state (though, in principle, it could be hidden in the large background). The low energy (~1 eV) integral cross section strongly scales as the bond length is stretched, and this could indicate a virtual state pole, since dipole supported bound states are not expected at the geometries addressed here.     

Theoretical study of NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> interacting with carbon nanotube

This paper deals with quantum mechanical interaction of no ₃⁻ with (5,5) and (8,0) swcnts. To perform this we have made an ab initio calculation based on the density functional theory. In these framework the electronic density plays a central role and it was obtained of a self-consistent field form. It was observed through binding energy that NO₃⁻ molecule interacts with each nanotube in a physisorption regime. We propose these swcnts as a potential filter device due to reasonable interaction with NO₃⁻ molecule. Besides this type of filter could be reusable, therefore after the filtering, the swcnts could be separated from NO₃⁻ molecule.