title: Conformational preferences of 3,4-dihydroxyphenylacetic acid (DOPAC).
abstract: The conformational space of 3,4-dihydroxyphenylacetic acid (DOPAC), an important dopamine metabolite, has been investigated by quantum chemical methods (B3LYP and MP2, with the 6-311++G(d,p) basis set) and matrix-isolation infrared spectroscopy. Detailed analysis of the calculated potential energy surfaces of the molecule led to identification of thirteen unique conformers, all of them showing the acetic acid side chain out of the aromatic ring plane by 60-95°. According to the calculated Gibbs energies, the five lowest energy conformers make up 99.7% of the conformational mixture at 298.15K, exhibiting individual populations falling between 16% and 24%. The main conformational trends of this molecule were interpreted on the grounds of a thorough analysis of the structural parameters and by the application of the Natural Bond Orbital theory. The role of the intramolecular interactions on the relative stability and structure of the conformers was also investigated. The infrared spectrum of DOPAC was registered after isolation of its monomers in argon and xenon matrices. Only one of DOPAC forms populated in the gas phase could be trapped in both matrix gases. This result is in agreement with the predicted low energy barriers for conformational isomerization and is also supported by annealing experiments. The spectra of matrix-isolated model compounds, phenylacetic acid and catechol, were studied under the same experimental conditions. These data were used as references and assisted in the interpretation of the results obtained for DOPAC.
authors.affiliation: Centre of Chemistry - Coimbra, Faculty of Pharmacy, University of Coimbra, 3000-548 Coimbra, Portugal. Electronic address: ajorge@qui.uc.pt.
authors.forename: A J
authors.initials: AJ
authors.lastname: Lopes Jesus
authors.affiliation: Centre of Chemistry - Coimbra, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal.
authors.forename: S
authors.initials: S
authors.lastname: Jarmelo
authors.affiliation: Centre of Chemistry - Coimbra, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal.
authors.forename: R
authors.initials: R
authors.lastname: Fausto
authors.affiliation: Centre of Chemistry - Coimbra, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal.
authors.forename: I
authors.initials: I
authors.lastname: Reva
mesh_terms: D015102:3,4-Dihydroxyphenylacetic Acid / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory
chemical_list: D015102:3,4-Dihydroxyphenylacetic Acid
keywords: 3,4-Dihydroxyphenylacetic acid (DOPAC); Energy barrier; Matrix-isolation infrared spectroscopy; Natural Bond Orbital analysis; Potential energy surface; Quantum chemical calculations