title: Synergic application of spectroscopic and theoretical methods to the chlorogenic acid structure elucidation.
abstract: Although chlorogenic acid (5-O-caffeoylquinic acid, 5CQA) is a dietary polyphenol known for its pharmacological and nutritional properties, its structural features have not been completely elucidated. This is the first study whose aim is to contribute to clarification of the 5CQA structure by comparing the experimental and simulated IR, Raman, (1)H NMR, (13)C NMR, and UV spectra. For this purpose, a comprehensive conformational analysis of 5CQA was performed to reveal its most stable conformations in the gas-state and solution (DMSO and methanol). The lowest-energy conformers were used to predict the spectra at two levels of theory: B3LYP-D3/and M06-2X/6-311+G(d,p) in combination with the CPCM solvation model. Both methods provide very good agreement between all experimental and simulated spectra, thus indicating correct arrangement of the atoms in the 5CQA molecule. The quinic moiety is characterized with directed hydrogen bonds, where the carboxylic hydrogen is not oriented towards the carbonyl oxygen of the carboxylic group, but towards the oxygen of the proximate hydroxyl group. In the gas-state the lowest-energy conformers are characterized with the O4H4⋯O9' hydrogen bond, whereas in the solvated state the structures with the O4H4⋯O10' hydrogen bond prevail. Knowing the fine structural details, i.e. the proper conformation of 5CQA, provides a solid base for all further investigations related to this compound.
authors.affiliation: Faculty of Science, University of Kragujevac, 12 Radoja Domanovića, 34000 Kragujevac, Serbia. Electronic address: mark@kg.ac.rs.
authors.forename: Svetlana
authors.initials: S
authors.lastname: Marković
authors.affiliation: Faculty of Science, University of Kragujevac, 12 Radoja Domanovića, 34000 Kragujevac, Serbia.
authors.forename: Jelena
authors.initials: J
authors.lastname: Tošović
authors.affiliation: Faculty of Physical Chemistry, University of Belgrade, 12-16 Studentski trg, 11000 Belgrade, Serbia.
authors.forename: Jasmina M
authors.initials: JM
authors.lastname: Dimitrić Marković
mesh_terms: D002726:Chlorogenic Acid / Q000031:analogs & derivatives* / Q000737:chemistry; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D011801:Quinic Acid / Q000031:analogs & derivatives* / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman
chemical_list: D002726:Chlorogenic Acid; D011801:Quinic Acid; C473200:5-caffeoylquinic acid
keywords: Chlorogenic acid; DFT calculations; NMR spectra; UV spectrum; Vibrational spectra