Combining DNA Barcoding and Chemical fingerprints to authenticate Lavender raw material.

OBJECTIVE: This study was initiated and conducted by several laboratories, 3 of the main cosmetic ingredient suppliers and 4 brands of cosmetics in France. Its objective is to show the interest and robustness of coupling chemical and genetic analyses in the identification of plant species. In this study, the Lavandula genus was used. METHODS: In this study, we used two analytical methods. Chemical analysis from UHPLC (ultra-high-performance liquid chromatography) and genetic analysis from barcoding with genetic markers. RESULTS: Eleven lavender species were selected (botanically authenticated) and analysed. The results show that three chemical compounds (coumaric acid hexoside, ferulic acid hexoside and rosmarinic acid) and three genetic markers (RbcL, trnH-psbA and ITS) are of interest for the differentiation of species of the genus lavandula. CONCLUSION: The results show that the combination of complementary analytical methods is a relevant system to prove the botanical identification of lavender species. This first study, carried out on a plant of interest for cosmetics, demonstrates the need for authentication using a tool combining genetic and chemical analysis as an advance over traditional investigation methods used alone, in terms of identification and authentication reliability.

OBJECTIF: Cette étude a été lancée et menée par plusieurs laboratoires, trois des principaux fournisseurs d'ingrédients cosmétiques et quatre marques de cosmétiques en France. Son objectif est de montrer qu'associer les analyses chimiques et génétiques dans l'identification des espèces végétales présente un intérêt et est une approche solide. Dans cette étude, c'est le genre Lavandula qui a été utilisé. MÉTHODES: Dans cette étude, nous avons fait appel à deux méthodes analytiques. L'analyse chimique, à partir de la chromatographie en phase liquide à haute performance (ultra-high-performance liquid chromatography, UHPLC), et l'analyse génétique en procédant à un codage à barres avec des marqueurs génétiques. RÉSULTATS: Onze espèces de lavande ont été sélectionnées (authentifiées du point de vue botanique) et analysées. Les résultats montrent que trois composés chimiques (acide coumarique hexoside, acide ferulique hexoside et acide rosmarinique) et trois marqueurs génétiques (RbcL, trnH-psbA et ITS) présentent un intérêt pour la différenciation des espèces du genre lavandula. CONCLUSION: Les résultats montrent que la combinaison de méthodes analytiques complémentaires est un système pertinent pour prouver l'identification végétale des espèces de lavande. Cette première étude, réalisée sur une plante qui offre un intérêt pour les cosmétiques, démontre la nécessité de procéder à une authentification à l'aide d'un outil qui conjugue analyse génétique et chimique ; elle représente une avancée par rapport aux méthodes d'investigation traditionnelles utilisées seules, en termes d'identification et de fiabilité de l'authentification.

Untargeted profiling of Glycyrrhiza glabra extract with comprehensive two-dimensional liquid chromatography-mass spectrometry using multi-segmented shift gradients in the second dimension: Expanding the metabolic coverage.

Metabolic profiling of Glycyrrhiza glabra using comprehensive two-dimensional liquid chromatography (LC × LC) coupled with photodiode array (PDA) and mass spectrometry (MS) detection is described. The separation was conducted under reversed-phase conditions, using a combination of first dimension (1 D) 150 mm microbore cyano column utilising 2.7 µm diameter (dp ) particles, and second dimension (2 D) 50 mm superficially porous octadecylsilica column with 2.7 µm dp particles. A multi-segmented shift gradient (MSG) for the 2 D separation was developed, and the orthogonality achieved was compared with other modes of gradients, such as full in-fraction, and shift gradient systems. Results demonstrated a significant expansion of metabolic coverage using MSG in 2 D, providing the highest measure of orthogonality compared to other gradient modes. Compound identifications were performed by employing complementary data from PDA and MS detection, with reference to structural group-type distribution in 2D space. A total of ca. 120 compounds were detected, and among them 37 were tentatively identified, distributed over the chemical families of glycosylated flavanones, triterpene saponins, and others. In comparison with one-dimensional LC, the total number of compounds detected was ca. 2-fold greater when LC × LC was employed. To the best of our knowledge, this is the first demonstration of the MSG mode in LC × LC, representing a powerful strategy to expand the metabolic coverage for analysis of plant-derived extracts, containing a multitude of different phytochemical classes.

Multiresidue analysis of multiclass pesticides in lavandin essential oil by LC/MS/MS using the scheduled selected reaction monitoring mode.

In this paper we describe the development of the first multiclass pesticide residue method applied to essential oils. A total of 70 pesticides covering a wide range of polarity and currently used on essential oil crops have been included in the method. The procedure consists of a 10-fold dilution of lavandin essential oil followed by a direct injection analysis by liquid chromatography/tandem mass spectrometry. The system used is an API 4000 QTrap equipped with an electrospray ionization interface and operating in scheduled selected reaction monitoring acquisition mode. Matrix effects were evaluated by comparing the slopes of matrix-matched and solvent-based calibration curves. Weak signal suppression or enhancement (<20%) was observed for most of the compounds. Method sensitivity was determined statistically by the injection of five matrix-matched calibration curves with the distribution's normality and the variance's homogeneity checked before establishment of a suitable regression model. Limits of detection (LODs) and quantification (LOQs) were then determined using the blank standard's deviation and the slope of the mean curve. The analytical method has been validated for 67 of the 70 pesticides and meets the following LOQs: ≤1 µg/L for 9 pesticides, ≤5 µg/L for 44, ≤10 µg/L for 9, and ≤20 µg/L for 5.

Synthesis and antiviral activity of new anti-HIV amprenavir bioisosteres.

Starting from the chemical structure of the recent FDA-approved anti-HIV drug Amprenavir (Agenerase), a potent HIV-protease inhibitor, we have designed new series of Amprenavir bioisoteres in which the methylene group of the benzyl group was replaced by a sulfur atom. This structural modification has required an original multistep synthesis. Unfortunately, introduction of the sulfur atom abolished or drastically decreased both inhibitory activity on recombinant HIV protease and HIV infection protection on MT4 cell cultures.

Contribution of chiral HPLC in tandem with polarimetric detection in the determination of absolute configuration by chemical interconversion method: Example in 1-(thi)oxothiazolinyl-3-(thi)oxothiazolinyl toluene atropisomer series.

We report the determination of the absolute configuration of eight stereoisomers in the series of chiral 1-(thi)oxothiazolinyl-3-(thi)oxothiazolinyl toluene atropisomers 1-3, from the known absolute configuration of one stereoisomer, determined by X-ray crystallography. The method uses the affiliation between signs of rotation of polarised light during chemical transformations which preserve the absolute configuration and also during rotation around a single pivot bond producing a compound of known configuration. The use of chiral HPLC in tandem with a chirality detector gives a decisive advantage since such correlation can be performed on a mixture of a very limited quantity of compounds, without tedious purification steps. The method shown as an example in this article, which uses chiral HPLC with chirality detection, may prove useful in many other cases where the determination of the absolute configuration is necessary and where a chemical interconversion method can be used on a microscale.