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1.
Analyst ; 148(24): 6228-6240, 2023 Dec 04.
Artículo en Inglés | MEDLINE | ID: mdl-37987708

RESUMEN

A new photoelectron spectroscopic method permitting a quantitative analysis of the volatile headspace of several essential oils is presented and discussed. In particular, we focus on the monoterpene compounds, which are known to be the dominant volatile components in many such oils. The photoelectron spectra of the monoterpene constituents may be effectively isolated by accepting for analysis only those electrons that accompany the production of m/z = 136 ions, and by using low photon energies that restrict cation fragmentation. The monoterpene isomers are then identified and quantified by regression modelling using a library of terpene standard spectra. An advantage of this approach is that pre-concentration of the volatile vapour is not required, and all steps are performed at ambient temperature, avoiding the possible deleterious effects (such as isomerisation/decomposition) that may sometimes arise in gas chromatographic (GC) procedures. As a proof-of-principle demonstration, three citrus oils (lemon, lime, bergamot) are analysed with this approach and the results are compared with reported GC composition profiles obtained for these oils. Potential advantages of the methodology that include multiplex detection and real-time, in situ analysis are identified and discussed. Alternative and faster experimental implementations concerning laboratory-based ionization and detection schemes are proposed and considered, as is the possibility of a straightforward extension towards simultaneous determination of enantiomeric excesses.

2.
Commun Chem ; 4(1): 72, 2021 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-36697576

RESUMEN

Proline is a unique amino-acid, with a secondary amine fixed within a pyrrolidine ring providing specific structural properties to proline-rich biopolymers. Gas-phase proline possesses four main H-bond stabilized conformers differing by the ring puckering and carboxylic acid orientation. The latter defines two classes of conformation, whose large ionization energy difference allows a unique conformer-class tagging via electron spectroscopy. Photoelectron circular dichroism (PECD) is an intense chiroptical effect sensitive to molecular structures, hence theorized to be highly conformation-dependent. Here, we present experimental evidence of an intense and striking conformer-specific PECD, measured in the vacuum ultraviolet (VUV) photoionization of proline, as well as a conformer-dependent cation fragmentation behavior. This finding, combined with theoretical modeling, allows a refinement of the conformational landscape and energetic ordering, that proves inaccessible to current molecular electronic structure calculations. Additionally, astrochemical implications regarding a possible link of PECD to the origin of life's homochirality are considered in terms of plausible temperature constraints.

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