Interaction of glyphosate in matrices of cellulose and diethylaminoethyl cellulose biopolymers: theoretical viewpoint of the adsorption process.

Glyphosate is an herbicide widely used in agricultural activities causing contamination of soils and bodies of water and damage to the biodiversity of ecosystems. In this context, the present study aimed to theoretically study the adsorption potential of the biopolymer cellulose (CE) and its diethylaminoethyl cellulose derivative (DEAEC) with the herbicide glyphosate (GLY). Theoretical calculations were performed using the density functional theory. Molecular electrostatic potential and frontier molecular orbital analyses were performed, which allowed identifying the possible sites of interaction of biopolymers that were in the functional groups -OH and O- of cellulose and in the groups -O- and -NH+(CH2CH3)2 of the DEAEC. Reactivity indices chemical softness and hardness showed that both adsorbents could interact with adsorbate. Simulated IR indicated that the interactions could be evinced in experimental measurements by changes in the bands of glyphosate (ν(P = O), δ(P-O-H), δ(C-N-H)) or in the bands of CE and DEAEC (ν(C-O), ν(C-H), ν(N-H)). The binding energies showed that the GLY interacts more effectively with CE than DEAEC. The ΔH prove that all processes are exothermic and the CE-GLY1 interaction showed value of ΔG < 0. The topological results showed a greater number of interactions with electrostatic nature. The results found in the study show that the theoretical data provides useful information to support the use of biopolymers as matrices for glyphosate adsorption or other contaminants.

Theoretical study of internal rotational barriers of electrons donating and electrons withdrawing groups in aromatic compounds.

The presence of internal rotation in sigma bonds is essential for conformational analysis of organic molecules and its understanding is of great relevance in chemistry, as well as in several other areas. However, for aromatic compounds that have substituent groups, withdrawers or donors of electron, there are no data in the literature to explain their rotational barriers. In this context, the work studied the internal rotational barriers of electron donating and withdrawing groups in aromatic compounds using the MP3, MP4, and CCSD(T) methods and the influence of substituents' nature on barrier heights was investigated through calculations based on the theory of Natural Bond Orbitals (NBO) and Quantum Theory of Atoms in Molecules (QTAIM). The results obtained showed that the CCSD(T) method is the one that best describes the internal rotational barriers, followed by MP4 and MP3 and the electron donating groups decrease the barrier, whereas electron withdrawing groups increase. Through the NBO analysis it was possible to observe that for withdrawing groups the interaction of the molecular orbitals is more accentuated promoting the increase of the rotational barrier of these compounds. Through the QTAIM analysis it was possible to show that, for electron donating groups, the internal rotation is influenced by the loss of electronic density when the substituents is perpendicular to the ring plane, however, for withdrawing groups the density is little influenced, regardless of the two conformations (minimum and maximum energy). Two molecules showed free rotation, trichloromethylbenzene and methylbenzene, and the theoretical calculations NBO and QTAIM showed that for these species there is no difference in the properties studied when there is rotation of the dihedral angle.