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Updated: Feb 21, 2026

Interfacial Molecular-level Structures of Polymers and Biomacromolecules Revealed via Sum Frequency Generation Vibrational Spectroscopy
Published on: August 13, 2019
Structure Determination, Conformational Flexibility, Internal Dynamics, and Chiral Analysis of Pulegone and Its
Anna Krin1,2,3, Cristóbal Pérez1,2,3, Pablo Pinacho4
1Deutsches Elektronen-Synchrotron, Notkestrasse 85, 22607, Hamburg, Germany.
Abstract:
In the current work we present a detailed analysis of the chiral molecule pulegone, which is a constituent of essential oils, using broadband rotational spectroscopy. Two conformers are observed under the cold conditions of a molecular jet. We report an accurate experimentally determined structure for the lowest energy conformer. For both conformers, a characteristic splitting pattern is observed in the spectrum, resulting from the internal rotation of the two non-equivalent methyl groups situated in the isopropylidene side chain. The determined energy barriers are 1.961911(46) kJ mol-1 and 6.3617(12) kJ mol-1 for one conformer, and 1.96094(74) kJ mol-1 and 6.705(44) kJ mol-1 for the other one. Moreover, a cluster of the lowest energy conformer with one water molecule is reported. The water molecule locks one of the methyl groups by means of a hydrogen bond and some secondary interactions, so that we only observe internal rotation splittings from the other methyl group with an internal rotation barrier of 2.01013(38) kJ mol-1 . Additionally, the chirality-sensitive microwave three-wave mixing technique is applied for the differentiation between the enantiomers, which can become of further use for the analysis of essential oils.
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