Linear retention index approach applied to liquid chromatography coupled to PDA and QqQ MS detectors for reliable characterization of oxygen heterocyclic compounds in essential oils and finished cosmetic products

Regulation (EC) n.1223/2009 of the European Parliament includes furocoumarins (FC) in the list of substances prohibited in cosmetic products except for normal content in natural essences used, the limit in sun protection and bronzing products is 1 mg/Kg [1]. Despite the official regulations the Scientific Committee on Consumers Products (ISCC) and the International Fragrance Association (IFRA) are still proposing the maximum content of psoralens in rinse-off and leave-on products, according to the latest evidences of phototoxicity [2,3]. To date, LC coupled to PDA detector is the main technique employed for FC determination. However, the high Limits of Quantification (LOQs) suggested by IFRA, limit the HPLC-PDA application to the analysis of essential oils, making necessary the development of a more sensitive HPLC-MS method for the analysis of FC at trace level in the finished cosmetic products [4]. This work provides a detailed analysis of PDA LOQs calculated for several oxygen heterocyclic compounds, among FC, coumarins, and polymethoxyflavones. The linear retention index approach was used, for the first time, together with the UV library, as an extra criterion for the reliable characterization of the target compounds in the essential oils. The LRI of specific volatile compounds were calculated in order to identify the interfering compounds of the matrix which affect the LOQs. Calibration curves were created in pure solvent and by adding the standard compounds to different blank samples, with the aim to overcome the matrix effect. Moreover, LRI was applied to a new more sensitive HPLC-QqQ MS method, with MS and MS/MS (Multiple Reaction Monitoring) libraries and external calibration. The MS method was validated and used to determine the content of FC in cosmetics, such as perfumes and body wash

Coumarins, Psoralens and Polymethoxyflavones in Cold-pressed Citrus Essential Oils: a Review

Cold-pressed Citrus essential oils namely lemon, bergamot, lime, grapefruit, mandarin, sweet and bitter orange are obtained from the peel of Citrus fruits. They were normally used in food, cosmetic, and pharmaceutical industries as ingredients. Essential oils extraction processes produce oils with different sensory qualities, and often these processes are expensive and have a low yield. For such a reason adulteration process are frequent, so careful attention must be paid to ensure the oils' genuineness and authenticity. Moreover, psoralen levels are continuously monitored by opinions and regulations released from International Fragrance Association and the European Parliament due to their photoactivity. This review aims to browse the scientific literature of the past 30 years on the characterization of the non-volatile fraction of cold-pressed Citrus essential oils to discuss results achieved so far and highlight future prospect

Differentiation of Italian extra virgin olive oils by rapid evaporative ionization mass spectrometry

Abstract The present work aims to differentiate Italian extra virgin olive oils through the analysis of about 100 samples for the building of a spectral database useful for the comparison beetwen top-quality oils. High-quality oils belonging to two different harvest years and coming from different Italian regions, labelled as PDO (Protected Denomination of Origin) or obtained from a single variety of olives (monocultivar), were available. Rapid Evaporative Ionization Mass Spectrometry, in combination with a monopolar handpiece as sampling device was explored for the first time on liquid and poorly conductive samples. Multivariate analyses were applied to build different chemometric models. The monocultivar oils gave positive feedback, leading to the reliable identification of each cultivar. The recognition of PDO oils resulted more challenging (failure percentage > 5%), probably due to the major intra-class variability, since oils labelled with the same PDO trademark often are produced from different cultivar in different percentages

Influence of Citrus Flavor Addition in Brewing Process: Characterization of the Volatile and Non-Volatile Profile to Prevent Frauds and Adulterations

In the last few years, the flavored beer market has increased significantly. In particular, consumers showed a growing interest in citrus-flavored beers. Citrus fruits contain, among other class of compounds, terpenes and terpenoids and oxygenated heterocyclic compounds. The absence of a specific legislation concerning beer flavored production and ingredients reported on the labels makes these beers subject to possible adulterations. Solid phase micro extraction (SPME) followed by gas chromatographic–mass spectrometry (GC-MS) and gas chromatographic-flame ionization detector (GC-FID) analysis of the volatile profile together with the characterization of the oxygen heterocyclic compounds through high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) demonstrated to be a powerful analytical strategy for quality control. In this study, we combined the volatile and non-volatile profiles of “citrus flavored mainstream beers”, in order to evaluate the authenticity and determine markers to prevent food frauds. The changes in the aroma composition of the unflavored types after the addition of peel, or citrus essential oil were also evaluated. The linear retention index (LRI) system was used for both techniques; in particular, its application in liquid chromatography is still limited and represents a novelty. The coupling of the high sensitivity of the HPLC MS/MS method with the LRI system, it has made possible for the first time a reliable identification and an accurate quantification of furocoumarins in citrus-flavored beers

Dietary Intake of Coumarins and Furocoumarins through Citrus Beverages: A Detailed Estimation by a HPLC-MS/MS Method Combined with the Linear Retention Index System

: Official regulations concerning the maximum number of substances in food are introduced as a consequence of possible adverse effects, after oral administration. In this regard, analytical methods are necessary in order to determine specific targets. Among oxygen heterocyclic compounds (OHCs, that are furocoumarins, coumarins and polymethoxyflavones), only coumarin is subject to restriction by the Regulation (EC) No 1334/2008 of the European Parliament. Furocoumarins are known for their phototoxicity and other side effects due to their dietary intake; however, an official limit about the maximum content of these compounds in food is still missing. The lack of information about the real amount of these compounds in food is responsible for the conflicting opinions about the introduction of an official limit. The HPLC-MS/MS method here proposed, in combination with the linear retention index system, represents an innovative analytical strategy for the characterization of OHCs in citrus beverages. Several types of drinks were analysed in order to quantify 35 OHCs in total. This method is suitable for the quality control of OHCs in food and the obtained results may be considered as informative data useful for the regulatory authorities in the emission of new opinions and for a potential new regulation in this field