Plastic additives are introduced in plastic material formulations, along with organic polymers, to offer different properties such as stability, plasticity or color. However, plastic additives may migrate from the plastic material to the content (in case of plastic containers) or to the material in contact with the plastic, like human skin. In the case of plastic medical devices, this migration is of particular interest, as plastic additives may be deleterious to health. In the present paper, we examined the interest of combining supercritical fluid extraction (SFE) to supercritical fluid chromatography (SFC) hyphenated to mass spectrometry (MS) in an online system to characterize plastic additives in laboratory gloves, taken as samples of medical devices. A set of target compounds comprising 18 plasticizers, 4 antioxidants and 2 lubricants was defined and their detectability with MS was examined, where it appeared that electrospray ionization (ESI) provided better detectability than atmospheric pressure chemical ionization (APCI). After examining possible stationary phases with the help of Derringer desirability function, an isocratic chromatographic method (CO₂:methanol 95:5) was developed on Shim-pack UC Phenyl column. The extraction method was examined with a 3-level full factorial design of experiments to optimize the extraction temperature (40 °C) and pressure (200 bar). The online SFE-SFC-MS method was compared to offline methods where the samples were extracted with liquid solvents at atmospheric pressure or high pressure then analysed with SFC-MS. In all cases, offline methods showed significant contaminants (like the oleamide lubricant) issuing from laboratory plastic materials as nitrogen drying station, syringes and filters, while the online method allowed a complete elimination of laboratory contaminations. Furthermore, the online method saved time, solvents and laboratory consumables. It will also show that transferring a compressible fluid from a loading loop is favourable to high efficiency, as the resulting chromatographic peaks are much thinner than when transferring a liquid. Compared to injecting liquid heptane, the efficiency increase was 3.4-fold, while compared to injecting liquid methanol (a common practice in SFC), the efficiency increase was 13-fold. Finally, the additive composition of different laboratory gloves was compared.

Almond okara, a by-product of almond milk production, is rich in bioactive components, such as polyphenols, lipids, and alpha-tocopherol, making it a valuable functional food ingredient. This work aimed to investigate its composition while exploring two main aspects: (i) the impact of extraction time, solid-to-solvent ratio, ethanol concentration, and temperature on polyphenol recovery, and (ii) the quantification of okara’s triglycerides (TG) and alpha-tocopherol contents. The polyphenols’ optimal extraction conditions were 90 min, a 1:30 solid-to-solvent ratio (w/v), 50% ethanol, and 60 °C. These conditions achieved a total polyphenol yield of 523 mg GAE, tannin yield of 340 mg GAE, total flavonoid yield of 548 mg CE, and a total antioxidant capacity of 779 mg AAE per 100 g dry okara. The Peleg model effectively described the extraction kinetics. Additionally, TG levels, quantified by UHE/LPSFC-APCI-MS, in okara were comparable to those in almonds, and alpha-tocopherol levels, quantified by LC-UV, were 14,400 µg/100 g in almonds and 15,600 µg/100 g in okara. These findings highlight the potential of okara as a valuable resource, with a straightforward, scalable, and cost-effective solid-liquid extraction (SLE) method for polyphenols and a supercritical fluid extraction method for TG, for use in the functional food, nutraceutical, and cosmetic industries.

Annatto, obtained from the seeds of achiote (Bixa orellana L.), is a widely used orange pigment rich in bixin and other apocarotenoids. This work reports the optimisation of a green extraction method of pigments and antioxidant compounds from achiote as well as its integration in a one-step green extraction-cosmetic formulation process. A biphasic solvent system of water and oil was used to recover simultaneously polar polyphenols, and less polar compounds, such as δ-tocotrienol and bixin. The optimisation of the ultrasound assisted extraction is presented, as well as a comparison of different vegetable oils used as extraction solvents. The composition, physicochemical properties and antioxidant activity of the oils were studied and their extraction performance was compared. Refined sunflower oil proved to be a better solvent than virgin olive, jojoba, coconut and grapeseed oils. Both aqueous and oil phases displayed an interesting antioxidant capacity. The oil phase contained 0.9% of bixin, as well as minor apocarotenoids and δ-tocotrienol. Twelve compounds, mainly phenolics, were identified by UHPLC-DAD-HRMS/MS in the aqueous phase. Twenty-one volatile compounds were identified in the volatile fraction by SPME-GC-MS. Lastly, a one-step green process is proposed to combine the extraction and the cosmetic formulation of the bioactive compounds.

Plastic materials are composed of polymers with small-molecule additives introduced in the composition during manufacturing to adapt the properties of the final product to its intended use. However, plastic additives may migrate into contact matrices. In the case of medical devices, the contact matrices may be biofluids or medical solutions to be infused to the patient. However, among plastic additives, some have recognized toxicity. Their possible migration is therefore a significant health concern. In this work, a method using Stir-Bar Sorptive Extraction (SBSE) was developed to extract and concentrate leachables from medical solutions. The stir-bar with adsorbed compounds was then placed in a supercritical fluid extraction system, to desorb the analytes with supercritical CO₂ and transfer them to supercritical fluid chromatography hyphenated to mass spectrometry (SFE-SFC-MS). Different medical solutions and devices were examined as nutritive bags, saline solution bottle, pipette, pre-filled syringe and an infusion tubing. Using this method, different plastic additives leaching from the packaging were found in medical solutions, including lubricants (oleamide and erucamide), plasticizers (DIBP, DBP, DEHP and DINCH) and antioxidants (Irgafos 168 and its oxide). In addition, a closed circuit was set up to imitate the process of patient infusion, to extract and detect leachables from plastic tubing used in infusion devices. A rinsing and contamination checking method was developed using the same SFE-SFC-MS system to easily reuse the SBSE device from one experiment to another and to facilitate sample preparation steps. Finally, the greenness of the sample preparation technique was evaluated with CACI and AGREEprep green scores.

Développement de méthodes en SFE-SFC-MS en ligne pour caractériser les additifs plastiques et leur migration à partir de dispositifs médicaux: De nos jours, les matériaux plastiques occupent une place centrale dans notre société. Depuis 2016, plus de 400 millions de tonnes de plastiques sont produits chaque année dans le monde pour des utilisations variées telles que les emballages, la construction, le transport ou l'électronique. Cette surproduction et surconsommation soulève des enjeux à la fois économiques, environnementaux et toxicologiques. Les plastiques sont constitués de polymères auxquels sont incorporées des molécules, principalement organiques, appelées additifs plastiques, destinées à modifier les propriétés physico-chimiques du matériau final. Cependant, un risque majeur lié à l'utilisation de ces additifs réside dans leur migration potentielle vers les matrices en contact, d'autant que certains d'entre eux sont classés comme Cancérigènes, Mutagènes ou Reprotoxiques (CMR), ou comme perturbateurs endocriniens. L'utilisation de dispositifs médicaux plastiques dans le secteur hospitalier est donc particulièrement préoccupante, en raison des migrations vers les fluides biologiques ou solutions médicales, puis vers l'organisme des patients. Face à la diversité croissante des additifs utilisés, de nombreuses méthodes d'extraction et d'analyse se développent. Parmi elles, l'utilisation de fluides supercritiques pour l'extraction (SFE) ou la chromatographie (SFC), couplées à la spectrométrie de masse (MS), constituent des techniques alternatives et complémentaires aux approches conventionnelles offrant des avantages en termes de diffusivité, d'efficacité et de sélectivité. Cette thèse a pour objectif le développement du couplage SFE-SFC-MS afin d'extraire et d'analyser les différents additifs plastiques entrant dans la composition des dispositifs médicaux. Par ailleurs, la combinaison de ce couplage avec l'extraction par sorption sur barreau magnétique (SBSE) propose une méthode innovante pour l'étude des interactions contenant-contenu dans les matrices médicales et biologiques.