Investigation of the torsional barrier of EDOT using molecular mechanics and DFT methods.

When heterocyclic monomers are polymerized by electrochemical or chemical methods, they form fully conjugated polymers which have a wide range of applications due to their outstanding electronic properties. Among this class of compounds, thiophene derivatives are widely used due to their chemical stability and synthesis flexibility. With the goal to investigate the torsion barrier of polymer chains, a few units of 3,4-ethylenedioxythiophene (EDOT) were chosen and submitted to molecular mechanics (MM), density functional theory (DFT) and coupled cluster CCSD(T) calculations. This study helps to understand the performance and transferability of force fields used in molecular mechanics and molecular dynamics simulations often used to describe structure-property relationships of those systems. Determination of inter-ring torsion angle was performed in a comparative study using both force field, DFT and CCSD(T) methods. A good agreement was noticed between MM and QC results and highlights the importance of the description of the interactions involving the oxygen atoms present in the structure of EDOT. These observations are related to the α,α-coupling that occurs between the monomer units and yields a linear polymer. DFT HOMO and LUMO orbitals were also presented. Finally, UV-vis spectra of EDOT units were obtained using several levels of theory by means of time-dependent DFT calculations (TD-DFT).

Thermal and electrical properties of starch-graphene oxide nanocomposites improved by photochemical treatment.

Bionanocomposite films have been prepared by casting an aqueous suspension of acetylated starch (ST) and poly(vinyl alcohol) (PVA) loaded with graphene oxide (GO). A photochemical and reagentless method has been successfully performed to convert the GO phase into reduced graphene oxide (RGO). The nanocomposites have displayed improved thermal and electrical properties when the amount of the GO phase is increased and properly converted to RGO. The molecular-level interactions between components are mainly hydrogen-bonding type according to attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Raman spectroscopies, as well as thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) has confirmed the effective mixing between the GO and the ST-PVA matrix. The thermal diffusivity and electrical resistivity of ST-GO nanocomposites have increased one order and decreased two orders of magnitude, respectively, after the photochemical treatment. These findings have confirmed the effectiveness of the proposed approach to produce starch-based nanocomposites with improved thermal and electrical properties.