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Intramolecular interactions (O-H∙∙∙O, C-H∙∙∙N, N-H∙∙∙π) in isomers of neutral, cation, and anion dopamine molecules: A DFT study on the influence of solvents (water and ethanol)

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Abstract

Context

Dopamine (DA) is one of the most important neurotransmitters associated with numerous neural disorders. This investigation reports the intramolecular interactions present in the isomers of neutral (DA0), anionic (DA−), and cationic (DA+) dopamine isomers in gas, water, and ethanol mediums. Neutral and anion isomers have O-H∙∙∙O, C-H∙∙∙N intramolecular hydrogen bonds and N-H∙∙∙π interactions. All the interactions are electrostatic in nature. Isomers of cation dopamine show no intramolecular interactions in the solvent. Natural charges from natural bond orbital (NBO) analysis show that O-H∙∙∙O bonds and the N-H∙∙∙π interactions are the most and least polar, respectively. 1H NMR study reveals the inverse linear correlation between shielding constant and electron density in a solvent medium. HOMO-LUMO energy gap indicates higher stability for neutral and cationic forms of dopamine isomers in water and ethanol medium.

Methods

We have optimized all the structural forms of dopamine molecule using the Becke three hybrid exchange and Lee-Yang-Parr correlation functional with Grimme’s dispersion correction, B3LYP-D3(BJ), and aug-cc-pVTZ basis set using the Gaussian16 software. Vibrational frequency analysis with no imaginary frequencies confirms the nature of global minima. The solvent studies (water and ethanol) were carried out using the SCRF keyword and the polarisable continuum model (PCM) of Miertus and Tomasi. NBO analysis and NMR studies were also performed for all conformers. Topology analysis was explored using the software Multiwfn.

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  1. Department of Physics, Bharathiar University, Coimbatore, Tamil Nadu, 641016, India

    Thekkayil Sangeetha & Senthilkumar Lakshmipathi

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  1. Thekkayil Sangeetha
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T. Sangeetha: conceptualization, methodology, formal analysis, writing — review and editing; Senthilkumar Lakshmipathi: conceptualisation, methodology, formal analysis, writing — review and editing.

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Correspondence to Senthilkumar Lakshmipathi.

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ESM 1:

All optimized geometries in gas and solvents, geometrical parameters of neutral, cation, and anion dopamine molecules, calculated electronic energy and energy gap, dipole moment, Natural charge of proton acceptor (q1) and proton donor (q2) NMR studies, optimized geometry coordinates (cartesian) of all dopamine molecular conformers are given in supplementary information. (DOCX 5433 kb)

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Sangeetha, T., Lakshmipathi, S. Intramolecular interactions (O-H∙∙∙O, C-H∙∙∙N, N-H∙∙∙π) in isomers of neutral, cation, and anion dopamine molecules: A DFT study on the influence of solvents (water and ethanol). J Mol Model 29, 67 (2023). https://doi.org/10.1007/s00894-023-05466-y

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