Bond order effects on the optoelectronic properties of oxygen/sulfur functionalized adamantanes.

The objective of this work, is to study adamantanes and to tune their bandgap, since pure adamantane is considered as an insulator due to its high bandgap energy. For this, we doped adamantane with oxygen and sulfur atoms, thus obtaining 730 different structures with double bonds and 730 different structures with single bonds, for a total of 1460 structures, and compared their properties. Among all, 31 molecules were selected that best represented the reduced bandgap behavior. The calculations with greater precision in its results were made using the Local Density Approximation (LDA), in the Density-Functional Theory (DFT) formalism, with PWC functional and TNP basis set. The electronic and optical properties were analyzed, by calculating the energy gap and absorption spectrum. Importantly, we observed that molecules doped with sulfur atoms (double bonds) had their energy gap reduced significantly compared to molecules doped with sulfur and/or oxygen atom with single bonds and pristine adamantane. It was found that in the absorption spectrum, the sulfur-doped structures had their spectrum shifted to the visible region, a fact that becomes relevant for potential dyes and optoelectronic applications. From the seven selected functionalized adamantanes (ADD-04, ADD-05, ADD-07, ADD-19, ADD-20, ADD-41, and ADD-48), any of these could be used as a dye. However, the ADD-20 molecule in particular, which presented optical absorption near (RGB) primary colors, could indicate a potential quantum dot material for application in developing screens of various electronic devices.

Cubane and cubanoid: Structural, optoelectronic and thermodynamic properties from DFT and TD-DFT method.

In this paper, we report structural, electronic and optical properties of cubane (C8H8) and cubanoids (cubane-like molecules) using Density Functional Theory (DFT). The cubanoids are cubanes for which Carbon atoms have been substituted by Nitrogen (N), Phosphorus (P), Boron (B), Silicon (Si), Arsenic (As), Antimony (Sb) or Bismuth (Bi) atoms. These molecules presented exceptional stability with several different symmetry point groups, being the majority Td. All calculated vibrational frequencies are positive for any studied molecules indicating that all these structures are in a stable state. The HOMO-LUMO gaps and DOS were calculated converged towards to values between 1.87 eV and 5.61 eV, actually showing promising electronic properties (Just for comparison, the cubane energy gap is 7.50 eV). The optical absorptions were also calculated for the cubanoid structure using the Time-Dependent Density Functional Theory (TD-DFT). Their dependence on the wavelength is analyzed, where five of theses structures absorb on the visible region. Finally, the extrapolation of thermodynamic properties indicates that these cubanoid could be potentially synthesized spontaneously, where four structures, the synthesis would occur for temperatures below 400 K, while for Si4Bi4H4 structure, the synthesis would occur at room temperature.

Conformational, Optoelectronic and Vibrational Properties of the Entacapone Molecule: A Quantum Chemistry Study.

A quantum chemistry study were carried out looking for the conformational, optoelectronic and vibrational properties of the entacapone molecule, an efficient drug used in the Parkinson's disease treatment. Classical annealing was performed to explore the entacapone's molecular configurations, searching for optimal geometries. The quantum optimization calculations were made using three different functional combination levels of the density functional theory (DFT). The structural data (bond length, bond and torsion angles), charge population analysis (absorption spectra) and molecular orbital study (HOMO and LUMO) were obtained considering the lower energy optimized conformation of the entacapone molecule. Furthermore, a complete assignment of the harmonic vibrational frequencies were achieved through their infrared (IR) and Raman spectra.

Pro- and Anticonvulsant Effects of the Ant Dinoponera quadriceps (Kempf) Venom in Mice.

Epilepsy affects at least 50 million people worldwide, and the available treatment is associated with various side effects. Approximately 20-30% of the patients develop seizures that persist despite careful monitored treatment with antiepileptic drugs. Thus, there is a clear need for the development of new antiepileptic drugs, and the venoms can be an excellent source of probes. In this context, while there are studies on venoms from snakes, scorpions, and spiders, little is known regarding venom from ants. The aim of this study was to investigate the potential pro- and anticonvulsant effects of the venom from the ant Dinoponera quadriceps (Kempf) in Swiss mice. After the injection of the crude venom (DqTx-5, 50, and 500 mg/mL) in the lateral ventricle of mice, we observed a reduction of exploration and grooming behaviors, as well as an increase in immobility duration. In addition, the crude venom induced procursive behavior and tonic-clonic seizures at the highest concentration. Conversely, the preadministration of the denatured venom (AbDq) at the concentration of 2 mg/mL protected the animals against tonic-clonic seizures (66.7%) and death (100%) induced by administration of bicuculline. Taken together, the findings demonstrate that D. quadriceps venom might be potential source of new pro- and anticonvulsants molecules.

Anhydrous crystals of DNA bases are wide gap semiconductors.

We present the structural, electronic, and optical properties of anhydrous crystals of DNA nucleobases (guanine, adenine, cytosine, and thymine) found after DFT (Density Functional Theory) calculations within the local density approximation, as well as experimental measurements of optical absorption for powders of these crystals. Guanine and cytosine (adenine and thymine) anhydrous crystals are predicted from the DFT simulations to be direct (indirect) band gap semiconductors, with values 2.68 eV and 3.30 eV (2.83 eV and 3.22 eV), respectively, while the experimentally estimated band gaps we have measured are 3.83 eV and 3.84 eV (3.89 eV and 4.07 eV), in the same order. The electronic effective masses we have obtained at band extremes show that, at low temperatures, these crystals behave like wide gap semiconductors for electrons moving along the nucleobases stacking direction, while the hole transport are somewhat limited. Lastly, the calculated electronic dielectric functions of DNA nucleobases crystals in the parallel and perpendicular directions to the stacking planes exhibit a high degree of anisotropy (except cytosine), in agreement with published experimental results.

Nanopercolation.

We investigate through direct molecular mechanics calculations the geometrical properties of hydrocarbon mantles subjected to percolation disorder. We show that the structures of mantles generated at the critical percolation point have a fractal dimension df approximately 2.5. In addition, the solvent access surface As and volume Vs of these molecules follow power-law behavior, As approximately L(alphaA) and Vs approximately L(alphaV), where L is the system size, and with both exponents alphaA and alphaV being significantly dependent on the radius of the accessing probing molecule, r(p). Our results from extensive simulations with two distinct microscopic topologies (i.e., square and honeycomb) indicate the consistency of the statistical analysis and confirm the self-similar characteristic of the percolating hydrocarbons. Due to their highly branched topology, this new class of disordered molecules can be of potential use in a variety of practical applications.