Estimation of the π–π interactions of aromatic amino acids in the phase of solution and sorbent using quantum chemical modeling
Abstract
Quantum chemical modeling of the π–π interactions between amino acids with an aromatic radical in their structure in various phases is carried out in this work. Aromatic amino acids phenylalanine and tryptophan and sorbents with a hydrophobic aromatic matrix, such as styrene-divinylbenzene ion exchangers and super-crosslinked sorbents based on this polymer, were studied. Quantum chemical modeling was performed using the Gaussian 09 program using the DFT electron density functional method with a hybrid B3LYP functional and a 6-31G++(d,p) basis with GD3 correction using the PCM method with correction of the superposition error of the basic set (BSSE) according to the Beuys–Bernardi procedure.
As established by modeling amino acid dimers in solution, the energy values and geometry obtained are consistent with the classical concepts of the π–π bond. The phenylalanine dimer formed by the π–π interactions of the benzene rings of the side radical can exist in two variants – a parallel offset and a T-shaped arrangement of the benzene rings. Tryptophan is characterized by the existence of three dimer variants. In addition to the two mentioned, a T–shaped "heteroatom ring" variant is implemented, in which one of the tryptophan molecules is oriented by the heteroatom of the side radical (the nitrogen atom of the indole cycle) to the center of the benzene ring of the side radical of the other tryptophan molecule. The parallel offset arrangement option is more advantageous for both amino acids, however, the T-shaped "heteroatom ring" variant characteristic of tryptophan is also characterized by high energy, which distinguishes this amino acid and requires consideration when studying various systems with its participation.
Whenmodeling the formation of the secondsorptionlayerdue to π–πsorbate–sorbateinteractions, systemsconsistingofthreesorbentmatrixelementparticlesandtwoamino acid molecules are considered. As aresult of modelingsystemswith the participation of phenylalanineinallmethods of combiningstartingfragments, it is shownthatstructureswithparallelarrangement of rings are formed,displacedrelative to each other.Whenmodeling the secondtryptophansorptionlayerin the sorbent, it was found thatadoubleT-shapedarrangementinvolvingsix-and five-memberedsideradicalcyclesofbothamino acid moleculesor a structureformedfromthreetriangularT-interactions of tryptophanradicals is realized.
It has been found that the formation of π–π bonds in a multiparticle system is energetically more advantageous than the formation of a single bond, since the number of π–electrons involved in the formation of a single multilayer π-electron system is greater, while multiple π–π interactions are least affected by substituents in the benzene ring.
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