Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Abstract

Studying the self‐assembly of uracil derivatives has great importance for biochemistry and nanotechnology. For example, modification of the sorbent surfaces by 5‐hydroxy‐6‐methyluracil (HMU) enhances their adsorption activity. It is assumed that these changes are caused by the self‐assembly of the network‐like supramolecular associates of the uracil derivative on the sorbent surface. In the present work, the relative stabilities of 15 hydrogen‐bonded dimers HMU have been studied by the TPSSh/TZVP density functional theory method and the strengths of the noncovalent interactions analyzed in terms of the reduced density gradient and natural bond orbital approaches. It was found that the symmetric dimer stabilized by two intermolecular hydrogen bonds N1–H∙∙∙O–C2 (dimer 1‐1) is the most stable. This suggests that the self‐assembly of HMU should occur through the intermediate formation of the dimer 1‐1. The results may be useful for understanding the processes of self‐assembly of the uracil derivatives and the rationalized design of the uracil‐based supramolecular structures with specific properties.

Understanding the Self-Assembling Behavior of Biological Building Block Molecules: A Spectroscopic and Microscopic Approach

“…using FLIM (Figure c). They have focused mainly on 5-halo derivatives because of their high significance. − Previously, research related to nucleobases mainly was conducted through theoretical and crystallographic approaches , whereas the assembling behaviors of nucleobase analogues in solution open up the opportunity to tune the properties for the experimentalists also. DCM shows a relatively greater increase in fluorescence intensity in three halo-uracils (i.e., 5-ClU, 5-BrU, and 5-IU).…”

Molecular design of all nitrogen pentazole‐based high energy density compounds with oxygen balance equal to zero

“…Understanding energetic materials, chemical, and mechanical behaviors better theoretically gradually attracted people's attention. It has been proved that theoretical studies based on quantum chemical treatment have been approved as a much useful research tool for screening the candidates of HEDCs, which not only provide the possibility for us to screen candidate compounds, but can also reveal the relationships between the molecular structure and performance.…”

“…The pentazolyl‐based compounds have high density, high heat generation, high gas generation, and low sensitivity, and are detonation products. Thus, they are promising to become efficient, safe, and environmentally friendly candidates for HEDCs . Today, research on the pentazolyl compounds as potential energetic materials has been attracting great attention.…”