δ18O compound-specific stable isotope assessment: An advanced analytical strategy for sophisticated adulterations detection in essential oils - Application to spearmint, cinnamon, and bitter almond essential oils authentication.

Natural plant extracts are primarily used as raw materials in the cosmetic and perfumery industry. However, adulterations with petrochemical products are occurring in the market, leading to non-100% natural products. Several analytical techniques such as impurity detection or enantioselective ratio assessments have been previously described as good indicators to detect any addition of synthetic products, but these techniques are ineffective with novel type of synthetic pathways such as semisynthesis. In order to improve authentication, development of advanced analytical strategies such as δ18O stable isotopic ratios assessment was tested on spearmint, cinnamon and bitter almond essential oils major metabolites (carvone, (E)-cinnamaldehyde, and benzaldehyde). Natural δ18O mean values (δ18OCarvone = 18.4‰; δ18OCinnamaldehyde = 13.9‰; δ18OBenzaldehyde = 16.5‰) were found to be higher than semisynthetic origin for the 3 studied molecules (δ18OCarvone = 9.2‰; δ18OCinnamaldehyde = 8.8‰; δ18OBenzaldehyde = 10.9‰). These measurements proved to be efficient to discriminate natural and semisynthetic origins of these components and therefore potentially lead to a novel way to authenticate natural products.

Determination of enantiomeric and stable isotope ratio fingerprints of active secondary metabolites in neroli (Citrus aurantium L.) essential oils for authentication by multidimensional gas chromatography and GC-C/P-IRMS.

Neroli essential oil (EO), extracted from bitter orange blossoms, is one of the most expensive natural products on the market due to its poor yield and its use in fragrance compositions, such as cologne. Multiple adulterations of neroli EO are found on the market, and several authentication strategies, such as enantioselective gas chromatography (GC) and isotope ratio mass spectrometry (IRMS), have been developed in the last few years. However, neroli EO adulteration is becoming increasingly sophisticated, and analytical improvements are needed to increase precision. Enantiomeric and compound-specific isotopic profiling of numerous metabolites using multidimensional GC and GC-C/P-IRMS was carried out. These analyses proved to be efficient for geographical tracing, especially to distinguish neroli EO of Egyptian origin. In addition, δ2H values and enantioselective ratios can identify an addition of 10% of petitgrain EO. These results demonstrate that enantioselective and stable isotopic metabolite fingerprint determination is currently a necessity to control EOs.

Chemical composition of French mimosa absolute oil.

Since decades mimosa (Acacia dealbata) absolute oil has been used in the flavor and perfume industry. Today, it finds an application in over 80 perfumes, and its worldwide industrial production is estimated five tons per year. Here we report on the chemical composition of French mimosa absolute oil. Straight-chain analogues from C6 to C26 with different functional groups (hydrocarbons, esters, aldehydes, diethyl acetals, alcohols, and ketones) were identified in the volatile fraction. Most of them are long-chain molecules: (Z)-heptadec-8-ene, heptadecane, nonadecane, and palmitic acid are the most abundant, and constituents such as 2-phenethyl alcohol, methyl anisate, and ethyl palmitate are present in smaller amounts. The heavier constituents were mainly triterpenoids such as lupenone and lupeol, which were identified as two of the main components. (Z)-Heptadec-8-ene, lupenone, and lupeol were quantified by GC-MS in SIM mode using external standards and represents 6%, 20%, and 7.8% (w/w) of the absolute oil. Moreover, odorant compounds were extracted by SPME and analyzed by GC-sniffing leading to the perception of 57 odorant zones, of which 37 compounds were identified by their odorant description, mass spectrum, retention index, and injection of the reference compound.