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Deep eutectic solvents (DESs) are a mixture of hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) molecules that can consist, respectively, of natural plant metabolites such as sugars, carboxylic acids, amino acids, and ionic molecules, which are for the vast majority ammonium salts. Media such as DESs are modular tools of sustainability that can be pointed toward the extraction of bioactive molecules due to their excellent physicochemical properties, their relatively low price, and accessibility. The present review focuses on the application of DESs for protein extraction and purification. The in-depth effects and principles that apply to DES-mediated extraction using various renewable biomasses will be discussed as well. One of the most important observations being made is that DESs have a clear ability to maintain the biological and/or functional activity of the extracted proteins, as well as increase their stability compared to traditional solvents. They demonstrate true potential for a reproducible but more importantly, scalable protein extraction and purification compared to traditional methods while enabling waste valorization in some particular cases.

International audience; Rice bran (RB) corresponds to the outer layers of whole grain rice and contains several phenolic compounds (PCs) that make it an interesting functional food ingredient. PC richness is enhanced in pigmented RB varieties and requires effective ways of extraction of these compounds. Therefore, we investigated conventional and deep eutectic solvents (DES) extraction methods to recover a wide array of PCs from red and black RB. The RB were extracted with ethanol/water (60:40, v/v) and two DES (choline chloride/1.2-propanediol/water, 1:1:1 and choline chloride/lactic acid, 1:10, mole ratios), based on Generally Recognized as Safe (GRAS) components. Besides the quantification of the most typical phenolic acids of cereals, nontargeted metabolomic approaches were applied to PCs profiling in the extracts. Globally, metabolomics revealed 89 PCs belonging to flavonoids (52%), phenolic acids (33%), other polyphenols (8%), lignans (6%) and stilbenes (1%) classes. All extracts, whatever the solvents, were highly concentrated in the main phenolic acids found in cereals (37–66 mg/100 g in black RB extracts vs. 6–20 mg/100 g in red RB extracts). However, the PC profile was highly dependent on the extraction solvent and specific PCs were extracted using the acidic DES. The PC-enriched DES extracts demonstrated interesting DPPH scavenging activity, which makes them candidates for novel antioxidant formulations.

The object of this thesis was to create models for two applications which readily appear in separation chemistry, namely the solid-liquid and the liquid-liquid extractions. The benefit of modelling in both cases is twofold. Studying the fundamental properties of ions and their solvation properties in the complex media, and simplifying the expression for important effects, enables us to construct the framework which can be used by both chemists in the laboratory, as well as the chemical engineers in the process design. For two applications we adapted two different systems, both of which can be considered as complex. The model system to study the solid-liquid separation were TiO2 nanotubes dispersed in the aqueous solution. This system was studied by the means of Classical Density Functional Theory coupled with the charge regulation method, within the Grand-canonical ensemble. Indeed, the method proved to be successful in establishing the full description of the charge properties of TiO2 nanotubes. In this case, we were interested in obtaining the description of ion inside the charged nanotubes under influence by the electric field (exhibited by nanotubes). Calculations predicted effects such as the difference in surface charge between the outer and the inner surface, or the violation of electroneutrality inside the nanotubes. It was demonstrated that the model was in the agreement with the experimental data. Moreover, the method can be directly used to predict titration for various techniques. A simple generalization of the proposed approach can be used to study the actual adsorption efficiency of the solid-liquid separation process. The model system to study the liquid-liquid extraction process included three distinct parts. The three parts were devoted to the cases on non-ionic, acidic ion exchangers, and finally the synergistic mixtures of extractants. Simple bulk statistical thermodynamics model, in which we incorporated some of the well-established concepts in colloidal chemistry provided a soft-matter approach for the calculation of actual engineering-scale processes. Were have expanded a classical simple equilibria approach to broader, more intuitive polydisperse aggregates formation that underlines the liquid-liquid extraction. The key finding can be presented as a current opinion or newly-proposed paradigm: at equilibrium, many aggregates completely different in composition but similar in free energy coexist. With obtained polydispersity, we were equipped with a tool to study a more 'global' behavior of liquid-liquid extraction. This urged us to pass our considerations of historical extraction isotherms to extraction 'maps'. Great care was devoted to the study of synergy since it is a 60-year old ongoing question in the separation industrial and science community. To our best knowledge, the first quantitative rationalization total synergistic extraction was proposed within this thesis. Underlying effects of enthalpy and entropy control on the organic phase structuring were decoupled and studied in detail. Hopefully, this thesis demonstrated the importance of mesoscopic modelling to assist both chemists and chemical engineers in practical examples.; Le but de cette thèse était de créer des modèles pour deux applications qui apparaissent couramment en chimie séparative, à savoir la séparation solide-liquide et la séparation liquide-liquide. L'avantage de la modélisation est manifeste dans les deux cas. L'étude fondamentale des propriétés des ions et de leur solvatation dans les milieux complexes, en tenant compte de façon simplifié des différents effets mis en jeu, nous a permis de construire un cadre qui utile aussi bien aux chimistes en laboratoire qu’aux ingénieurs lors de la conception des procédés. Nous avons adapté cette stratégie sur deux systèmes différents, qui peuvent tous deux être considérés comme complexes. Le premier système modèle pour étudier la séparation solide-liquide était des nanotubes de TiO2 dispersés dans une solution aqueuse. Ce système a été étudié au moyen de la Théorie de la Fonctionnelle de la Densité Classique couplée à une méthode de régulation de charge, au sein de l'ensemble Grand-Canonique. La méthode s'est avérée efficace pour établir la description complète des propriétés de charge des nanotubes de TiO2. Dans ce cas, nous nous sommes intéressés à obtenir la description de l'ion à l'intérieur des nanotubes chargés sous l'influence du champ électrique (créé par les nanotubes). Les calculs ont prédit des effets tels que la différence de charge de surface entre la surface externe et la surface interne, ou la violation de l'électroneutralité à l'intérieur des nanotubes. Il a été démontré que le modèle était en accord avec les données expérimentales. De plus, la méthode peut être utilisée directement pour prédire diverses techniques de titrage. Une simple généralisation de l'approche proposée permettra d'étudier l'efficacité d'adsorption réelle du procédé de séparation solide-liquide. Le second système modèle concerne l'étude du procédé d'extraction liquide-liquide et il comprend trois parties distinctes. Les trois parties ont été consacrées aux cas des extractants non ioniques, puis acides (échangeurs d'ions), et enfin aux mélanges synergiques d'extractants. Un modèle simple de thermodynamique statistique, dans lequel nous avons incorporé certains des concepts bien établis en chimie colloïdale, a fourni une approche de type matière molle pour calculer le processus à l'échelle de l'ingénieur. Nous avons développé une approche classique d'équilibres simples pour une compréhension plus large et plus intuitive de la formation des agrégats polydisperses dans l'extraction liquide-liquide. La principale conclusion présentée est que l’on doit proposer un nouveau paradigme pour la chimie : à l'équilibre, de nombreux agrégats de composition très différente mais similaires en énergie libre, coexistent. Avec la polydispersité obtenue, nous avons ainsi proposé un outil pour étudier un comportement plus "global" de l'extraction liquide-liquide. Cela nous a poussés à passer des considérations classiques d'isothermes d'extraction à celles plus précises des " cartes " d’extraction. Un grand soin a été apporté à l'étude de la synergie puisqu'il s'agit d'une important question depuis 60 ans dans la communauté scientifique et industrielle de la séparation. A notre connaissance, la première rationalisation quantitative de la synergie d’extraction a été proposée dans le cadre de cette thèse. Les effets sous-jacents des contrôles enthalpique et entropique sur la structuration des phases organiques ont été découplés et étudiés en détail. Nous espérons que cette thèse a démontré l'importance de la modélisation mésoscopique sur des exemples pratiques utilisés à la fois par les chimistes et les ingénieurs.

This study assesses, qualitatively and quantitatively, the performance of ten bio-based solvents to replace hexane for the extraction of oil from Pistacia lentiscus edible fruits. Solvent screening was achieved through theoretical approach using the COnductor-like Screening MOdel for Realistic Solvation (COSMO-RS) predictions and an experimental protocol based on GC-FID and HPTLC analysis. Unsupervised multivariate analyses were performed on GC-FID and HPTLC data. Experiments corroborated theoretical predictions indicating that MeTHF was the best alternative solvent to replace hexane. Moreover, the obtained extract exhibited a good anti-inflammatory activity, inhibiting by 91.9% NO release in RAW 264.7 macrophages. These findings highlighted the potential of green solvents especially MeTHF in lipid extraction and exhibited that P. lentiscus oil presents a potential anti-inflammatory property and great nutritional value, notably high amount of oleic and linoleic acid, thus encouraging its valorization in food, cosmetic or pharmaceutical industry., Cette étude consiste à évaluer, qualitativement et quantitativement, la performance de dix agro-solvants afin de remplacer l’hexane pour l’extraction de l’huile à partir des fruits comestibles de Pistacia lentiscus. Le criblage des solvants a été réalisé par une approche théorique en utilisant des outils de prédiction tels que COSMO-RS et une approche expérimentale basée sur les analyses CG-DIF et HPTLC. Des analyses multivariées ont été effectuées sur les données CG-DIF et HPTLC. Les résultats expérimentaux ont confirmé les prédictions théoriques indiquant que le MeTHF était le meilleur solvant alternatif pour substituer l’hexane. En outre, l’extrait obtenu présentait une bonne activité anti-inflammatoire, inhibant de 91,9% la libération de NO dans les macrophages RAW264.7. Ces résultats ont mis en évidence le potentiel des solvants verts, en particulier du MeTHF dans l’extraction lipidique et ont montré que l’huile de P. lentiscus présentait une activité antiinflammatoire potentielle et une grande valeur nutritionnelle, notamment une teneur élevée en acide oléique et linoléique, encourageant ainsi sa valorisation dans les industries alimentaire, cosmétique ou pharmaceutique.

International audience; In recent years, almost all extraction processes in the perfume, cosmetic, pharmaceutical, food ingredients, nutraceuticals, biofuel and fine chemical industries rely massively on solvents, the majority of which have petroleum origins. The intricate processing steps involved in the industrial extraction cycle makes it increasingly difficult to predict the overall environmental impact; despite the tremendous energy consumption and the substantial usage of solvents, often the yields are indicated in decimals. The ideal alternative solvents suitable for green extraction should have high solvency, high flash points with low toxicity and low environmental impacts, be easily biodegradable, obtained from renewable (non‐petrochemical) resources at a reasonable price and should be easy to recycle without any deleterious effect to the environment. Finding the perfect solvent that meets all the aforementioned requirements is a challenging task, thus the decision for the optimum solvent will always be a compromise depending on the process, the plant and the target molecules. The objective of this comprehensive review is to furnish a vivid picture of current knowledge on alternative, green solvents used in laboratories and industries alike for the extraction of natural products focusing on original methods, innovation, protocols, and development of safe products.

Les tourteaux de colza et de tournesol, principalement utilisés en alimentation animale pour leur forte teneur en protéines, représentent des sources d'acides phénoliques aux propriétés antioxydantes et bioacives variées mais peu valorisées à ce jour. Par ailleurs, les procédés de séparation de ces composés sont basés sur des extractions par solvants qui génèrent des effluents et impactent l'intégrité des autres composants des matières premières. La première partie de ce travail de thèse a été consacrée au développement de nouveaux procédés de séparation de la fraction phénolique des tourteaux de colza et de tournesol. Après un broyage adéquat des tourteaux, le fractionnement par tri électrostatique et turbo-séparation a permis d'obtenir des fractions enrichies en protéines et composés phénoliques. Dans les deux cas, l'état granulométrique des tourteaux broyés a été déterminant. Le tri électrostatique a conduit aux plus forts taux d'enrichissement en protéines et composés phénoliques (jusqu'à deux fois la concentration dans les tourteaux) avec des rendements de l'ordre de 30% après recyclages. Cette étape a été suivie par l'extraction de la fraction phénolique par des mélanges hydro-alcooliques " verts " à base d'éthanol, en substitution au méthanol. Dans la deuxième partie, nous nous sommes intéressés à la production enzymatique des acides sinapique et caféique, à partir des tourteaux ou de leurs extraits. Trois cinnamoyl estérases recombinantes d'A. niger aux activités et spécificités différentes ont été testées. L'hydrolyse des tourteaux non traités thermiquement s'est traduite par une dégradation des composés phénoliques par des enzymes endogènes. Le problème a pu être contourné en réalisant l'hydrolyse sur l'extrait phénolique des tourteaux avec néanmoins, dans le cas du colza, l'existence de réactions secondaires néfastes au rendement en acide sinapique. La dernière partie a consisté en la synthèse de mono- et di-esters d'acide sinapique et caféique avec différents α,ω-diols aliphatiques, puis l'évaluation de leur capacité antioxydante en milieu émulsionné et en milieu homogène. Un effet négatif de la mono-estérification des acides phénoliques a été observé en milieu hétérogène montrant ainsi l'influence négative du groupement hydroxyle situé à l'extrémité de la chaîne alkyle. Un effet de seuil a été observé, en revanche, avec les deux familles de di-esters d'acides phénoliques, indiquant une amélioration de la capacité antioxydante jusqu'à un optimum correspondant à une longueur de chaine alkyle particulière. Enfin, tous les mono- et di-esters testés en milieu homogène ont montré une capacité antiradicalaire plus faible que celle des acides phénoliques de départ correspondants.

The behaviour of actinides in the environment (in the surroundings of uranium miningsites, waste storage or contaminated sites) depends on the interaction of these elements with theorganic ligands present in these different systems. The interactions of actinides withpolyfunctional organic ligands could trap the element or inversely, favour their migration.In this work, the behaviour of actinides (III, V and VI) in aqueous solution was studied in thepresence of two polyaminocarboxylic ligands: nitrilotriacetic acid (NTA) and iminodiaceticacid (IDA).The study of the complexation of pentavalent protactinium by NTA and IDA was conductedaccording to a dual approach. A thermodynamic study carried out by liquid-liquid extraction inthe system TTA/Toluene/HClO4/NaClO4/Pa(V)/ligand, with protactinium at tracer scale (C233Pa< 10−10 M), has been implemented in order to determine the stoichiometry, the mean charge ofcomplexes and the associated formation constants. A structural approach with protactiniumin weighable quantity (C231Pa≈ 10−3 M) was conducted in order to determine the coordination geometry of complexes and interatomic distances.The variations of the distribution coefficient D of Pa(V) as a function of nitrilotriacetateconcentration enabled to determine that the maximum stoichiometry for the Pa-NTA and Pa-IDA systems is 2. For the Pa-NTA system, the two successive complexes predominant in theaqueous phase are a neutral species for (1:1) complex PaO(NTA) and charge -3 for the (1:2)which may correspond to PaO(NTA) -:R. In addition, Capillary Electrophoresis InductivelyCoupled Plasma Mass Spectrometry experiments have been performed to confirm the charge (-3) for the maximum stoichiometry complex. For the Pa-IDA system, the results have shownthe successive formation of two positive complexes PaO(IDA)3+ and PaO(IDA)+2. Optimized structures of Pa-NTA and Pa-IDA complexes were established using DFT or molecular dynamics calculations.The complexation of trivalent (Am and Cf) and hexavalent (Np and Pu) actinides with IDA was performed by Capillary Electrophoresis coupled with Inductively Coupled Mass Spectrometry(CE-ICP-MS). The variations of overall electrophoresis mobility of actinides species as function of CIDA2 allow the determination of the formation constants of actinides IDAcomplexes. The formation constants of complexes with (1:1) stoichiometry are reported forAm(III) and Cf(III). Concerning the complexes Np(VI) and Pu(VI) with iminodiacetic acid,formation constants of (1:1) and (1:2) stoichiometry complexes were determined; Le comportement des actinides dans l’environnement (site miniers, sites de stockagedes déchets et sites contaminés) dépend de l’interaction de ces éléments avec des ligandsprésents dans les différents milieux (air, sol, eaux superficielles et souterraines). Lesinteractions des actinides avec des ligands organiques polyfonctionnels peuvent piéger ceséléments ou au contraire favoriser leur migration.Dans ce travail, le comportement d’actinides aux degrés d’oxydation III, V et VI ensolution aqueuse a été étudié en présence de deux ligands polyaminocarboxyliques : l’acidenitrilotriacétique (NTA) et l’acide iminodiacétique (IDA).L’étude de la complexation du protactinium pentavalent par NTA et IDA a été conduiteselon une double approche : une étude thermodynamique réalisée par extraction par solvant,avec le protactinium à l’échelle des traces (C233Pa < 10-10 M) et une étude structurale, avecle protactinium en quantité pondérable (C231Pa ≈ 10-3 M), réalisée par Spectroscopied’Absorption des rayons X (SAX) et complétée par des calculs de chimie quantique.Les variations du coefficient de distribution de Pa(V) dans le systèmeTTA/Toluène/ HClO4 / NaClO4 /Pa(V)/ligand en fonction de la concentration de ligands àplusieurs températures et/ou acidités ont permis de déterminer la stœchiométrie maximale et lacharge moyenne des complexes Pa(V)-NTA et Pa(V)-IDA ainsi que les constantes de formationassociées à chaque espèce. Une stœchiométrie maximale de 2 a été observée pour les deuxsystèmes. Pour le système Pa-NTA, les deux complexes successifs prédominants dans la phaseaqueuse sont une espèce neutre PaO(NTA) pour le complexe (1:1) et une espèce de charge -3pour le complexe (1:2) qui pourrait correspondre à PaO(NTA) -:R. Une étude complémentairepar Electrophorèse Capillaire couplé à un spectromètre de masse (EC-ICP-MS) a permis deconfirmer la charge (-3) du complexe Pa − (NTA)-. Pour le système Pa-IDA, les résultats ontmontré la formation successive de deux complexes positifs PaO(IDA)3+ et PaO(IDA)+2.Lagéométrie de coordination et les distances interatomiques des complexes de stœchiométriemaximale ont été déterminés à partir de calculs DFT ou de dynamique moléculaire.L’étude de la complexation d’actinides trivalents (Am et Cf) et hexavalents (Np et Pu)par IDA a été réalisée par EC-ICP-MS. Les variations de la mobilité électrophorétique globaleen fonction de la concentration en IDA-R ont permis de déterminer les constantes de formationdes actinides avec IDA. Les constantes de formation des complexes de stœchiométrie (1:1)sont rapportées pour Am (III) et Cf (III). Concernant les complexes Np (VI) et Pu (VI) avecl'acide iminodiacétique, les constantes de formation des complexes de stœchiométriques (1:1)et (1:2) ont été déterminées.

The behaviour of actinides in the environment (in the surroundings of uranium miningsites, waste storage or contaminated sites) depends on the interaction of these elements with theorganic ligands present in these different systems. The interactions of actinides withpolyfunctional organic ligands could trap the element or inversely, favour their migration.In this work, the behaviour of actinides (III, V and VI) in aqueous solution was studied in thepresence of two polyaminocarboxylic ligands: nitrilotriacetic acid (NTA) and iminodiaceticacid (IDA).The study of the complexation of pentavalent protactinium by NTA and IDA was conductedaccording to a dual approach. A thermodynamic study carried out by liquid-liquid extraction inthe system TTA/Toluene/HClO4/NaClO4/Pa(V)/ligand, with protactinium at tracer scale (C233Pa< 10−10 M), has been implemented in order to determine the stoichiometry, the mean charge ofcomplexes and the associated formation constants. A structural approach with protactiniumin weighable quantity (C231Pa≈ 10−3 M) was conducted in order to determine the coordination geometry of complexes and interatomic distances.The variations of the distribution coefficient D of Pa(V) as a function of nitrilotriacetateconcentration enabled to determine that the maximum stoichiometry for the Pa-NTA and Pa-IDA systems is 2. For the Pa-NTA system, the two successive complexes predominant in theaqueous phase are a neutral species for (1:1) complex PaO(NTA) and charge -3 for the (1:2)which may correspond to PaO(NTA) -:R. In addition, Capillary Electrophoresis InductivelyCoupled Plasma Mass Spectrometry experiments have been performed to confirm the charge (-3) for the maximum stoichiometry complex. For the Pa-IDA system, the results have shownthe successive formation of two positive complexes PaO(IDA)3+ and PaO(IDA)+2. Optimized structures of Pa-NTA and Pa-IDA complexes were established using DFT or molecular dynamics calculations.The complexation of trivalent (Am and Cf) and hexavalent (Np and Pu) actinides with IDA was performed by Capillary Electrophoresis coupled with Inductively Coupled Mass Spectrometry(CE-ICP-MS). The variations of overall electrophoresis mobility of actinides species as function of CIDA2 allow the determination of the formation constants of actinides IDAcomplexes. The formation constants of complexes with (1:1) stoichiometry are reported forAm(III) and Cf(III). Concerning the complexes Np(VI) and Pu(VI) with iminodiacetic acid,formation constants of (1:1) and (1:2) stoichiometry complexes were determined; Le comportement des actinides dans l’environnement (site miniers, sites de stockagedes déchets et sites contaminés) dépend de l’interaction de ces éléments avec des ligandsprésents dans les différents milieux (air, sol, eaux superficielles et souterraines). Lesinteractions des actinides avec des ligands organiques polyfonctionnels peuvent piéger ceséléments ou au contraire favoriser leur migration.Dans ce travail, le comportement d’actinides aux degrés d’oxydation III, V et VI ensolution aqueuse a été étudié en présence de deux ligands polyaminocarboxyliques : l’acidenitrilotriacétique (NTA) et l’acide iminodiacétique (IDA).L’étude de la complexation du protactinium pentavalent par NTA et IDA a été conduiteselon une double approche : une étude thermodynamique réalisée par extraction par solvant,avec le protactinium à l’échelle des traces (C233Pa < 10-10 M) et une étude structurale, avecle protactinium en quantité pondérable (C231Pa ≈ 10-3 M), réalisée par Spectroscopied’Absorption des rayons X (SAX) et complétée par des calculs de chimie quantique.Les variations du coefficient de distribution de Pa(V) dans le systèmeTTA/Toluène/ HClO4 / NaClO4 /Pa(V)/ligand en fonction de la concentration de ligands àplusieurs températures et/ou acidités ont permis de déterminer la stœchiométrie maximale et lacharge moyenne des complexes Pa(V)-NTA et Pa(V)-IDA ainsi que les constantes de formationassociées à chaque espèce. Une stœchiométrie maximale de 2 a été observée pour les deuxsystèmes. Pour le système Pa-NTA, les deux complexes successifs prédominants dans la phaseaqueuse sont une espèce neutre PaO(NTA) pour le complexe (1:1) et une espèce de charge -3pour le complexe (1:2) qui pourrait correspondre à PaO(NTA) -:R. Une étude complémentairepar Electrophorèse Capillaire couplé à un spectromètre de masse (EC-ICP-MS) a permis deconfirmer la charge (-3) du complexe Pa − (NTA)-. Pour le système Pa-IDA, les résultats ontmontré la formation successive de deux complexes positifs PaO(IDA)3+ et PaO(IDA)+2.Lagéométrie de coordination et les distances interatomiques des complexes de stœchiométriemaximale ont été déterminés à partir de calculs DFT ou de dynamique moléculaire.L’étude de la complexation d’actinides trivalents (Am et Cf) et hexavalents (Np et Pu)par IDA a été réalisée par EC-ICP-MS. Les variations de la mobilité électrophorétique globaleen fonction de la concentration en IDA-R ont permis de déterminer les constantes de formationdes actinides avec IDA. Les constantes de formation des complexes de stœchiométrie (1:1)sont rapportées pour Am (III) et Cf (III). Concernant les complexes Np (VI) et Pu (VI) avecl'acide iminodiacétique, les constantes de formation des complexes de stœchiométriques (1:1)et (1:2) ont été déterminées.

Fruit and vegetables are rich in bioactive compounds that contribute to the prevention of a number of degenerative diseases. These components are also present, often in even higher concentrations, in the co-products from fruit and vegetable processing. Such fact, makes these co-products an attractive source for the extraction of bioactives, turning the extraction itself into an attractive valorization strategy for these co-products. There has been recently renewed interest in extraction methods, notably with a process intensification using physical phenomena and the search for alternative solvents. This paper will present the main bioactives in fruit and vegetables, and their co-products, and the precautions to preserve these molecules in the food processing chain, with a main focus on the pros and cons of recently proposed extraction developments, particularly on extraction mechanisms, sample pre-treatment, and solvent choice.

In recent years, the industrial sector of vegetable extraction has been evolving due to the growing interest of consumers for natural food ingredients combined with growing environmental concerns. Therefore, it seems essential to replace existing processes using toxic petroleum bases solvents with greener extraction processes with lower energy consumption, less wastes but higher extract quality. The objective of this thesis has consisted in the research and development of a new extraction process using liquefied gases as liquid solvents. First, this manuscript will outline the state of the art on the liquefied gases and how they are used for extraction of natural products. After this survey, 3 liquefied gases (n-butane, HFO-1234ze and DME) have been selected for laboratory scale experiments performed using a dedicated extraction unit whose design is detailed in chapter II. Then, the tests performed with these 3 gases for extraction of lipophilic compounds from several plant materials has been described. The experimental approach has been combined with a predictive one using decision tools: Hansen Solubility Parameters and COSMO-RS model. This survey demonstrated that liquefied gases are interesting solvents for solubilization and extraction of lipophilic compounds of interest. In parallel, the impacts of the process on environment, safety regulation and quality showed that liquefied gas extraction could be easily transposed at industrial scale., Depuis quelques années, le domaine de l’extraction végétale est en pleine mutation, avec à la fois un intérêt croissant des consommateurs pour des ingrédients d’origine naturelle, combiné à des préoccupations environnementales. Il apparaît dès lors indispensable de remplacer les procédés actuels utilisant des solvants pétrochimiques nocifs par de nouveaux procédés d’extraction réduisant le besoin énergétique, la toxicité du solvant et la quantité de déchets tout en s’assurant du rendement et de la qualité de l’extrait obtenu. L’objectif de cette thèse a donc consisté à développer un nouveau procédé d’extraction mettant en œuvre des gaz liquéfiés comme solvants. Ce manuscrit présentera tout d’abord l’état de l’art sur les gaz liquéfiés existants et leur mise en œuvre pour l’extraction des produits naturels. A l’issue de cette présentation, 3 gaz liquéfiés ont été sélectionnés (n-butane, HFO-1234ze et le DME) comme solvants pour mener des essais au laboratoire, grâce à un prototype dont la conception est détaillée dans le chapitre II. Dans un second temps, les essais réalisés à l’aide de ces gaz liquéfiés pour l’extraction de composés lipophiles ont été décrits. L’approche expérimentale a été couplée à une approche prédictive par l’utilisation d’outils d’aide à la décision : les paramètres de solubilité de Hansen et le modèle COSMO-RS. La prédiction théorique ainsi que les essais expérimentaux ont confirmé l’intérêt des gaz liquéfiés pour la solubilisation et l’extraction de composés lipophiles d’intérêt biologique et à haute valeur ajoutée. Parallèlement l’étude des impacts du procédé sur l’environnement, la qualité, la réglementation et la sécurité ont montré que l’extraction par gaz liquéfié était un procédé facilement transposable à l’échelle industrielle.

The actinide speciation in solution is central to the understanding and improvement of separation processes for the nuclear fuel cycle as well as envirronmental speciation problems. However, the radioactivity of these elements combined with their chemical complexity make the study of their speciation a real experimental challenge. That is why, bringing into play the molecular modeling may be a key help in getting new insights on this issue. In this work, coupling quantum chemical calculations to experimental data (thermodynamics, EXAFS, UV-visible spectroscopy) for studying plutonium(IV) speciation in an organic phase containing N,N-dialkylamide ligands enabled us to identify the formation of several complexes having different coordination modes of the ligand to the plutonium. In parallel, as no force field has been reported for discribing plutonium(IV) by classical molecular dynamics, we decided to tackle the development of such a potential for this element. This development has been initiated with the parameterization of actinide - water interactions considering the series from thorium to berkelium at their +IV oxidation state. The chosen ab initio parameterization approach as well as the final force field are presented. Then, the first molecular dynamics results are compared to available experimental data. Finally, the limits and future developments concerning both the parameterization approach and the analytical potential are discussed in detail.; L’étude de la spéciation des actinides en solution revêt une importance particulière à la fois pour la compréhension et l’amélioration des procédés de séparation pour le cycle du combustible nucléaire ainsi que pour les problèmes de spéciation dans l'environnement. Toutefois, leur caractère radioactif associé à la complexité de leur chimie fait de l’étude de la spéciation des actinides un véritable challenge expérimental. C’est pourquoi le recours à la modélisation moléculaire peut s’avérer une aide déterminante pour progresser sur cette thématique. Dans ce travail, le couplage de calculs de chimie quantique et de données expérimentales (thermodynamique, EXAFS, spectroscopie UV-visible) pour étudier la spéciation du plutonium(IV) en phase organique après extraction par des ligands N,N-dialkylamides nous a permis d'identifier la formation de plusieurs complexes ayant des modes de coordination du ligand au plutonium différents. Parallèlement, aucun champ de force n'ayant été reporté pour décrire le plutonium(IV) par dynamique moléculaire classique, nous avons entrepris de développer un potentiel d'interaction classique pour cet élément. Ce développement a été initié par le paramétrage des interactions de la série d'actinides du thorium au berkelium au degré d'oxydation IV dans l'eau. L'approche ab initio retenue pour le paramétrage ainsi que le champ de force résultant sont exposés. Les premiers résultats de dynamique moléculaire sont comparés aux données expérimentales disponibles dans la littérature puis les limites et perspectives d'amélioration de la méthode de paramétrage ainsi que du potentiel sont discutées en détail.ts clésChamp de forceActinides -- SpéciationPlutonium -- ComposésComplexes métalliquesDynamique moléculaireSpectrométrie EXAFSMéthodes ab initio (chimie quantique)Extraction par solvant

The green chemistry era has pushed the scientific community to investigate and implement new solvents in phenolic compounds (PC) extraction as alternatives to organic solvents, which are toxic and may be dangerous. Recently, deep eutectic solvents (DES) have been applied as extraction solvents for PC. They have the advantages of biodegradability and ease of handling with very low toxicity. Nevertheless, the extraction process is affected by several factors: affinity between DES and the target compounds, the water content, the mole ratio between DES’ starting molecules, the liquid/solid ratio between the DES and sample, and the conditions and extraction method. On the other hand, PC recovery from DES is a challenge because they can establish a strong hydrogen bond network. Alternatively, another possibility is to use DES as solvent extraction as well as formulation medium. In this way, DES can be suitable for cosmetics, pharmaceutical, or food applications.

International audience; Recent trends in food extraction techniques have largely focused on finding solutions that minimize the use of toxic solvents or to find alternatives for n-hexane. As an original solution, a new process for extraction of natural product using liquefied gases has been developed at laboratory scale. The applicability of this new process was demonstrated using n-butane as alternative solvent to n-hexane. Extraction of lipophilic natural products such as carrot oleoresin, caraway aromas and sunflower oil was assessed using liquefied n-butane. COSMO-RS simulations allowed determination of the relative solubility of the lipophilic compounds in liquefied n-butane and n-hexane. This theoretical approach was validated with extraction experiments on carrots, caraway seeds and sunflower seeds. Compositions of the extracts were comparable but the extract yields were lower using n-butane. For example the extraction yields were, with n-butane and with n-hexane respectively, 36.9% and 53.4% for sunflower seeds oil, 10.9% and 15.0% for caraway seed essential oil, 25.7% and 55.8% for carrots oleoresin. However the extracts obtained by using n-butane are directly free of solvents and also food grade, as it is an authorized solvent for foodstuff production.

International audience; This study was performed to compare, in term of quality and quantity, conventional and green lipid extraction procedures of three Tunisian date palm (Phoenix dactylifera L.) seeds cultivars (Deglet Nour, Allig and Belah). Extractions were performed using n-hexane and 2-methyltetrahydrofuran (MeTHF) as solvents. Identification and quantification of extracted fats and lipids were carried out by gas chromatography coupled with a flame ionization detector and high performance thin-layer chromatography. Results showed that Deglet Nour presents the highest lipids extraction yield (7.24–5.97%) using the both solvents. Hansen solubility simulation demonstrated that MeTHF is a good alternative solvent for lipid date seeds extraction. In addition, extraction of oils from date pits with ultrasound and micro-wave were better in terms of extraction time (30 min versus 8 h) comparing to soxhlet procedure and of extraction yield comparing to maceration (about 6% versus 4%). Triglycerides represent almost the whole recovered oils composition with 99% and the fatty acids were mainly oleic (44.02–46.9%), lauric (20.00–23.10%), myristic (8.88–11.26%), palmitic (9.00–10.73%) and linoleic (6.13–9.21%) acids.

Sub-critical water is widely accepted as an environmentally benign solvent, for extraction but also as a catalytic medium therefore has the potential to support processing of multiple components found in biomass. The manuscript demonstrates the versatility of sub-critical water as a generic medium to support hydrolysis of rice bran (carbohydrates) and sunflower oil (lipid substrates), substrates that possess very different physio-chemically properties within a continuous flow process configuration. Response surface methodologies (RSM) were used to assist modelling the multiple process parameters that impact sub-critical water mediate hydrolysis of sunflower oil. Successful validation, of the models illustrate that 100% FFA yield would be achieved at temperature 385 °C; pressure 20 MPa; residence time of 35 min; oil to water ratio 1:1.8 (v/v) represents 65% water. Experiments conducted under these conditions yielded 93.5%, thereby confirming the utility of the RSM as a tool to assist in process development.

Poster Session Wednesday : Theme 5: Production and regulatory aspects of herbal preparations; Solid/liquid extraction as key step for quality assessment of commercial cranberry products using HPTLC-densitometry. 9. Joint Natural Products Conference 2016

This research paper presents a quick and ecofriendly technique for the extraction of harpagoside (HS), the active marker of Harpagophytum procumbens (HP), along with a comparison with conventional methods so as to propose an efficient HPLC method. HP is widely used as an anti-inflammatory in phytotherapy. The quality control of the herbal drug and extract calls for a time consuming method of conventional extraction, which involves a high consumption of solvents. In this study, HP has been extracted using conventional ultrasound (UAE) and microwave (MAE)-assisted methods. The effects have been examined based on several parameters of HS extraction efficiencies. An HPLC method with a core-shell column was developed in order to calculate the HS in HP. The flow rate was reduced by 4. The method of validation used is specific, linear, precise and accurate. MAE and UAE saved solvent consumption, time and energy. It has, therefore, been found that the combined UAE-HPLC process is convenient and appropriate for the quality control of HP.

International audience; Lipid-based oleaginous microorganisms are potential candidates and resources for the sustainable production of biofuels. This study was designed to evaluate the performance of several alternative bio-based solvents for extracting lipids from yeasts. We used experimental design and simulation with Hansen solubility simulations and the conductor-like screening model for realistic solvation (COSMO-RS) to simulate the solubilization of lipids in each of these solvents. Lipid extracts were analyzed by high performance thin-layer chromatography (HPTLC) to obtain the distribution of lipids classes and gas chromatography coupled with a flame ionization detector (GC/FID) to obtain fatty acid profiles. Our aim was to correlate simulation with experimentation for extraction and solvation of lipids with bio-based solvents in order to make a preliminary evaluation for the replacement of hexane to extract lipids from microorganisms. Differences between theory and practice were noted for several solvents, such as CPME, MeTHF and ethyl acetate, which appeared to be good candidates to replace hexane.

International audience; This study evaluated the performance of alternative green solvents, i.e. D-limonene, dimethylcarbonate (DMC), ethanol, ethyl acetate, ethyl lactate and methyltetrahydrofuran (MeTHF) compared to the petroleum based dichloromethane, for extraction of alpha-mangostin from Garcinia mangostana pericarps. The Hansen solubility parameters (HSPs) were used to explain the dissolution behavior of the solutes and solvents, and the conductor-like screening model for realistic solvation. The (COSMO-RS), a statistical thermodynamic approach based on the results of quantum chemical calculations for comprehending the dissolving mechanisms were used to predict the extraction prediction. On the basis of the Hansen analysis, dichloromethane was the most suitable solvent for extraction of alpha-mangostin. However, COSMO-RS analysis showed a higher solubility of alpha-mangostin in ethyl lactate, DMC, MeTHF, ethyl acetate and ethanol. Moreover, the experimental studies using a classical reflux extraction followed by a quantitative HPLC analysis of alpha-mangostin showed similar results to the predictive values from the COSMO-RS model. The alpha-mangostin levels extracted by ethyl lactate, DMC, MeTHF, ethyl acetate and ethanol were higher than those using dichloromethane and D-limonene. The results support the potential use of ethyl lactate, DMC, MeTHF, and ethanol as alternative green solvents for the preparation of alpha-mangostin extracts.

The present study was designed to evaluate five green solvents, i.e. 2-methyltetrahydrofuran (2-MeTHF), dimethyl carbonate (DMC), cyclopentyl methyl ether (CPME), isopropyl alcohol (IPA) and ethyl acetate, for the substitution of n-hexane in the extraction of carotenoids from carrots. Initially, solvent selection was made through the theoretical physicochemical solvent properties and solubility results obtained using two simulation programs, Hansen Solubility Parameters (HSPs) and Conductor-like Screening Model for Realistic Solvation (COSMO-RS) which use a statistical thermodynamics approach based on the result of quantum chemical calculation, for comprehension of the dissolving mechanism. On the basis of the HSPs analysis, non-polar or slightly polar solvents were the most suitable solvents for extraction of carotenoids. COSMO-RS analysis showed a higher probability of solubility for all the carotenoids from carrot in CPME, 2-MeTHF and ethyl acetate compared with n-hexane. The experimental results using a conventional solid–liquid extraction by maceration showed that the best green solvents were CPME, 2-MeTHF and ethyl acetate in accordance with the predictive results from COSMO-RS. The highest carotenoid content (78.4 mg 100 g−1 DM) was observed in CPME where 66% was represented by β-carotene and 34% was α-carotene. These results support the potential of CPME and 2-MeTHF as alternative green solvents for extraction of carotenoids. This work was supported in part thanks to funding from the fellowship given to Edinson Yara Var´on (no. TECSPR14-2-0029) from the People Programme (Marie Curie Actions) of the Seventh Framework Programme of the European Union (FP7/ 2007–2013) under REA grant agreement no. 600388 (TECNIOspring programme), and from the Agency for Business Competitiveness of the Government of Catalonia, ACCI´O. The authors also are grateful to the Avignon University and Lleida University for the nancial and academic support.

National audience

Niobium (Nb) and tantalum (Ta) are two strategic elements for developed countries because of their unequalled properties and their use in several key sectors like the aerospace, fuel, building, nuclear, medical imaging or electronic industries. Due to their almost-identical chemical properties, the industrial processes currently used for the niobium-tantalum separation require strongly complexing media, like hydrofluoric acid. However, the high toxicity and the environmental footprint of these media force the industrials to develop new processes. In this regard, alkaline media represent a good alternative but the chemistry of Nb and Ta in such media is still poorly known. The objectives of this PhD thesis were to probe the speciation of Nb and Ta in alkaline aqueous solutions and to develop a new hydrometallurgical process able to perform the Nb-Ta separation. Firstly, new data were obtained on the speciation of Nb and Ta in alkaline media based on solubility measurements, UV-visible spectrophotometry, solid state NMR, Raman spectroscopy and capillary electrophoresis. Secondly, the information obtained from aqueous solutions (both synthetic and industrial) allowed us to develop an original solvent extraction process able to separate Nb and Ta without using any fluoride compound. This innovative process was tested at a pilot-scale (~ 1 L/h) on industrial solutions. The technical-economic evaluation of the developed process shows that this latter is profitable and economically competitive over the current industrial processes., Le niobium (Nb) et le tantale (Ta) sont deux éléments stratégiques pour les pays développés car ils sont difficilement substituables et utilisés dans de nombreux secteurs clés comme l’automobile, l’aéronautique, le nucléaire, le bâtiment, l’industrie pétrolière, l’imagerie médicale et l’électronique.La très grande similarité chimique du Nb et du Ta fait que les procédés industrialisés permettant leur séparation requièrent des milieux très complexants, comme les solutions d’acide fluorhydrique. Cependant, la toxicité et l’impact environnemental de ces solutions poussent les industriels à développer de nouveaux procédés. Les milieux alcalins peuvent être une alternative mais la chimie du Nb et du Ta à pH alcalin est encore peu connue à l’heure actuelle. Les objectifs de cette thèse étaient d’étudier la spéciation du Nb et du Ta dans les solutions aqueuses basiques et d’élaborer un procédé hydrométallurgique, sans fluor, pour la séparation niobium-tantale. Tout d’abord, de nouvelles données ont été acquises sur la spéciation du Nb et du Ta grâce à des mesures de solubilité, de spectrophotométrie UV-visible, de RMN du solide, de spectroscopie Raman et d’électrophorèse capillaire. Ensuite, les informations obtenues à partir de solutions aqueuses, synthétiques et industrielles, ont permis de développer un nouveau procédé d’extraction par solvant capable de séparer le Nb et le Ta et n’utilisant aucun réactif fluoré. Le procédé développé a également été testé et validé à l’échelle pilote (~ 1 L/h) sur des solutions industrielles. Enfin, l’étude technico-économique du procédé développé révèle que celui-ci sera rentable et compétitif par rapport aux procédés existants.

Extractives are present in much larger amounts in knotwood than in heartwood in the 12 tested hardwood and softwood species. The chemical identity of the extractives varies largely among species, lignans being only present in softwood species. Extractives from knotwood may constitute an important source of new chemicals and remain still poorly known. The content of extractives (and particularly lignans) in knots was compared to that of heartwood in a number of different European softwood and hardwood species. Twelve species characteristic of European forests were sampled. Extractions were carried out with four solvents of increasing polarity (dichloromethane, acetone, toluene/ethanol and water). Gas chromatography-mass spectrometry (GC-MS) was used for the identification of the compounds present in acetone extracts which are expected to contain lignans. In all tested species, knotwood presented larger contents of extractives than heartwood. The main compounds were lignans, stilbenes and flavonoids, lignans being present only in softwood species. With the exception of oak, knotwood in softwood species contain larger amounts of extractives than that in hardwood species. The chemical nature of extractives present in knotwood varies with species. Their amount is generally much higher in softwood than heartwood species.

Increasing number of dietary supplement containing cranberry polyphenols are commercialized every year. The composition of cranberry ingredients varies from whole fruit powder to cranberry extract or mixture with blueberry. In order to analyze the quality of cranberry based commercial products, researchers proceed to quality control based on BL-DMAC analysis after one step extraction. In our previous work, we demonstrated that BL-DMAC analysis is not sufficient alone to assess the quality of cranberry ingredients. BL-DMAC as quality control couple to High Performance Thin Layer Chromatography -densitometry bring complementary information, especially rate of epicatechin, PAC-A2and PAC-B2. In this work, different extraction solvents were screened for extraction of PACs from a range of commercial dietary supplements. Thus, solid / liquid extraction step was repeated until total extraction of polyphenols was achieved, i.e no coloration of the residue in contact with DMAC reagent. If the solvent nature was found to have a minor impact, the number of required extraction steps varied significantly between commercial products. This step was then demonstrated to be a key factor to control for meaningful comparison between various food supplements. Quality assessment of cranberry extracts was then conducted using both BL-DMAC and HPTLC-densitometry protocols, in order to obtain global PACs content and metabolic profile. A large diversity of PACs global content and profile was observed[br/] This work highlighted the need of new standardization protocols to control and asses the quality of cranberry ingredients, to guarantee biological effect.

Vegetable oils take a large part in industry for food and non-food applications. However the extraction process of oil from oilseeds includes a solvent extraction step using hexane. Despite its various advantages it presents numerous drawbacks; it is sourced from petroleum, it has a high flammability and it appears to be dangerous for health and environment (CMR2). This study presents a theoretical screening using COSMO-RS simulations of the relative solubility of vegetable oil constituents regarding several bio-based solvents as well as an experimental screening of the efficiency of these solvents. The aim is to correlate simulations and experiments and give a preliminary evaluation for the substitution of hexane by bio-based solvents for the extraction of vegetable oils. Differences between theory and practice have been noticed for several solvents such as terpenes that appeared to be good candidates in theory and that were in fact the solvents that gave the lowest extraction yield.

L’amélioration du rendement de l’extraction de l’huile à partir des grignons d’olive passe par la recherche de solvants efficaces et bon marché. Le rendement de l’extraction de l’huile à partir du grignon d’olive augmente en fonction de L’addition de l’acétone au trichloréthylène. Le mélange le plus intéressant semble être celui constitué de 75 % d’acétone et de 25 % de trichloréthylène. Dans ce cas, une augmentation de 37,5 % en matières grasses par rapport au trichloréthylène pur est observée. Les analyses effectuées montrent une augmentation des teneurs en insaponifiables et en phospholipides. L’analyse par chromatographie en phase gazeuse montre que les huiles extraites sont riches en acides gras insaturés et sont composées principalement d’acide oléique

Cette étude trace un profil des diverses technologies utilisées et en développement pour la séparation et/ou la récupération des métaux dans les effluents industriels. Les principes de fonctionnement de ces technologies sont abordés, ainsi que leurs avantages et limites d'utilisation. Les procédés d'enlèvement et de récupération des métaux comprennent les techniques de précipitation (formation d'hydroxydes, de carbonates, de sulfures, etc.) et coprécipitation (sels de fer et d'aluminium, etc.), d'adsorption (sable, cellulose, charbon activé, pyrite, ciment, lignite, mousse de tourbe, sciure de bois, etc.) et de biosorption (bactéries, levures, moisissures, algues marines et d'eaux douces), d'électrodéposition et d'électrocoagulation, de cémentation, de séparation par membranes (osmose inverse et électrodialyse), d'extraction par solvant (acides carboxyliques, amines aliphatiques ou aromatiques, acides aminés, composés phénoliques, phosphates alkyl, etc.), et d'échange d'ions (résines naturelles et synthétiques). La précipitation ou la coprécipitation représentent les procédés les plus largement utilisés et étudiés pour l'enlèvement des métaux des effluents industriels, suivis des techniques d'adsorption. Les procédés plus sophistiqués tels que l'électrodéposition, l'extraction par solvant, la séparation par membranes et l'échange d'ions, bien que largement utilisés dans les procédés métallurgiques, sont relativement peu employés et examinés pour le traitement des effluents industriels. La biosorption a fait l'objet de plusieurs travaux de recherche au cours des dernières années et représente une option intéressante pour le traitement de divers types d'effluents contenant de faibles concentrations en métaux. Finalement, le recyclage et la gestion optimale des effluents constitue une avenue de plus en plus suivie par les industries soucieuses de satisfaire aux nouvelles réglementations et législations., This study is dedicated to the review of the different technologies used and evaluated for the removal and/or recovery of metals from industrial effluents. The principles involved in these technologies are discussed, as well as the advantages and limits associated with these processes. The metal removal and recovery processes include the following techniques: precipitation, adsorption and biosorption, electrowinning and electrocoagulation, cementation, membrane separations, solvent extraction and ion exchange.Precipitation and coprecipitation are the most used and studied methods for metal removal from industrial waste waters. The method of precipitation used most often to remove metals from waste water consists of precipitating them in the form of hydroxides. The usual procedure involves the addition of chemicals such as lime (CaO or Ca(OH)2), Mg(OH)2, NaHCO3, Na2 CO3, (NH4)2 CO3, NaOH or NH4 OH. The precipitation of metals by carbonates or sulphides is an effective alternative to hydroxide precipitation. The use of carbonates allows the precipitation of metals to occur at pH values lower than those necessary with the hydroxides. Moreover, the precipitates thus formed are denser and have better characteristics of solid-liquid separation. Precipitation by sulphides is normally carried out with reagents such as: Na2 S, NaHS, H2 S or FeS. In acidic media, the lower solubility of metal sulphides (Cd, Co, Cu, Cr, Ni, Mn, Zn, etc.), makes it possible to reach concentrations lower than those obtained by precipitation as hydroxides. Coprecipitation with aluminum and iron salts is also an effective means for the removal of metals from effluents.Adsorption methods are also widely applied and examined for this purpose. However, in most cases the use of adsorbents requires an effluent neutralization step. Indeed, the neutralization of acid effluents must take place to allow their disposal in sewerage systems. A wide variety of adsorbents can be employed, both organic and inorganic: aluminum or iron oxides, sand, activated carbon, mixtures of coal and pyrite, iron particles, gravel or crushed brick, cement, etc. Studies have demonstrated the possibility of eliminating metals by adsorption on vegetable matter: peat moss, sawdust and wood bark, etc. Chitin and chitosan, two natural polymers that are abundant in the cell walls of fungi and shellfish, also have excellent properties of metal fixation. The utilization of different agricultural by-products (peanut skins, coconuts, corn cobs, onions skins, tea leaves, coffee powder, canola meal, etc.) for metal adsorption has also been proposed.Biosorption has been intensively studied in recent years as an economical treatment for metal recovery from dilute industrial effluents. Biosorption implies the use of live or dead biomass and/or their derivatives, which adsorb the metal ions with the ligands or functional groups located on the external surface of the microbial cells. Capacities for metal adsorption on various types of biomass (bacteria, yeasts, fungi, marine and freshwater algae) have been evaluated. The microorganisms used for the metal adsorption step must usually be immobilized in a matrix or in an easily recoverable support. The immobilizing agents or matrices most usually employed are alginate, polyacrylamine, polysulphone, silica gel, cellulose and glutaraldehyde.Electrowinning is a well-established technology that is widely employed in the mining and metallurgical industries (heap leaching, acid mine drainage, etc.), in metal transformation industries (wastes from plating and metal finishing), and in the electronics and electrical industries for the removal and/or the recovery of metals in solution. Many metals (Ag, Au, Cd, Co, Cr, Cu, Ni, Pb, Sn and Zn) present in the effluents can be recovered by electrodeposition using insoluble anodes.Electrocoagulation is another electrochemical approach, which uses an electrical current to remove several metals in solution. In fact, the electrocoagulation systems can be effective in removing suspended solids, dissolved metals, tannins and dyes. The contaminants present in waste water are maintained in solution by electrical charges. When these ions and the other charged particles are neutralized with ions of opposite electric charge, provided by a electrocoagulation system, they become destabilized and precipitate in a form that is usually very stable.Cementation is a type of precipitation method implying an electrochemical mechanism. In this process, a metal having a higher oxidation potential passes into solution (e.g., oxidation of metallic iron, Fe(0), to ferrous iron, Fe(II)) to replace a metal having a lower oxidation potential. Copper is the metal most frequently separated by cementation. However, the noble metals (Ag, Au and Pd), as well as As, Cd, Ga, Pb, Sb and Sn, can also be recovered in this manner.Reverse osmosis and electrodialysis are two processes using semipermeable membranes applicable to the recovery of metal ions. In electrodialysis, selective membranes (alternation of cation and anion membranes) fit between the electrodes in electrolytic cells. A continuous electrical current and the associated ion migrations, allow the recovery of metals. The techniques of membrane separation are very efficient for the treatment of dilute waste waters.The metallurgical industry has used solvent extraction for many years for a broad range of separations. This technique is employed today for the removal of soluble metals (Cd, Cr, Co, Cu, Ni, Mo, U, V, Zn, etc.) from waste water. Separation is carried out in contact with an immiscible organic phase to form salts or complex compounds, which give a favorable solubility distribution between the aqueous and organic phases. Various types of reagents can be used for the extraction: carboxylic acids, aliphatic or aromatic amines, amino acids, alkyl phosphates, phenolic compounds. The non-selective removal of metal contaminants in aqueous solutions can be obtained with a whole range of organic reagents. Promising new reagents have been proposed recently for the selective extraction of metals, such as Cd, Co, Cr and Zn.Ion exchangers are insoluble substances having in their molecular structure acidic or basic groups able to exchange, without modification of their physical structure, the positive or negative ions fixed at these groups. The first ion exchangers used were natural substances containing aluminosilicates (zeolites, clays, etc). Nowadays, the most-used ion exchangers are mainly organic in nature (resins). For the extraction of metals, the removal of cations in solution is usually done with the sulphonic acid group (-SO3- H+) of a polystyrene resin, or, with a chelating resin containing iminodiacetate functional groups. Ion exchange has recently received considerable attention for the separation and concentration of metals from waste water. These developments are especially applicable to the plating and metal transformation industries, for the removal of Cr, Co, Cu, Cd, Ni, Fe and Zn.The more sophisticated processes, such as electrowinning, solvent extraction, membrane separations and ion exchange, although frequently used in metallurgical processes, are less popular for wastewater treatment than are precipitation methods. Finally, recycling and optimal management of effluents constitutes an approach more and more widely applied by industries to satisfy new environmental regulations and laws.

The fundamental analysis and modeling of kinetics of solvent extraction of rapeseed oil enable the quantification of the “washing” and “diffusion” steps. Both are illustrated through “starting accessibility” and “effective diffusivity”, respectively. This is a relevant way to identify how to intensify and optimize the operating conditions in terms of highest yield and lowest extraction time. Using the instant controlled pressure drop (DIC) expansion as a pre-treatment for the intensification of the whole unit operation, the starting accessibility ratio reached a value of 28.69% against 19.03% for the raw material. Effective diffusivity of DIC treated samples reached a value of 2.05 × 10-12 m2/s instead of 0.72 × 10-12 m2/s for the raw material. Regarding oil composition, predominant fatty acids in all extracted rapeseed oils are oleic acid (C18:1 n9) ranged from 57.58 to 59.03%, linoleic acid (C18:2 n6) ranged from 21.23 to 21.89%, and linolenic acid (C18:3 n3) ranged from 9.11 to 9.45%. None of DIC treatment produced a significant variation in relative fatty acid profile.

International audience; The health problems amongst musical instrument makers working on the White mulberry (Morus alba), lead to investigate the toxicity potential of wood extractives. Five solvents of different polarity and two methods of extractions were used to ensure a thorough, clear and classified compound removal. The compounds were identified using qualitative GC-mass and the toxicity were determined by studying their effect on termite survival (Reticulitermes flavipes). The results indicated the presence of different compound categories like phenols, higher hydrocarbons, fatty acids, sterols and aromatic components in the extractives. These compounds were not removable by just one solvent and the order of removal was polarity related. The extractives were found toxic towards termites. Resorcinol, which corresponded to the highest proportion of peaks in the GC-mass spectra, has been assigned as the possible compound responsible for the allergic reactions by the artisans.

The extraction stage is considered to be a key step of most analytical strategies, as it greatly influences the type and quality of analytical data. In case of plants, which are interesting materials for a broad range of domestic or industrial-scale applications, extraction is a particularly crucial step as solid samples are considered most of the time. Indeed, extractions from solids are well known to be more critical than from liquids, owing to limitations by diffusion and/or strong solute–solid interactions; solutes may also be trapped into cells within the plant materials. Consequently, careful knowledge about the plant material itself (its structure and composition) and whenever possible about the compounds to be extracted (their expected levels, polarity, and stability) is of great help for conceiving and optimizing an extraction process; the fate of the extract is also important to consider, as the selectivity expected for the extraction differs between target and fingerprint approaches. Practically, even though several extraction techniques are available, none is the best and should be recommended for any application. However, the use of recent techniques should be favored, as they reduce both the solvent volume and the time required for the extraction; the hyphenation or combination of techniques should be investigated to take benefit from the advantages of several techniques. Keywords: extraction methodologies; extraction techniques; guidelines for extraction; plant materials; sample preparation; solid extraction; solute–matrix interactions; solute–solvent interactions

International audience; This present study was designed to evaluate the performances of five alternative solvents (alcohols: ethanol, isopropanol and terpenes:ρ-limonene, α-pinene, p-cymene) compared to η-hexane in rapeseed oil extraction. The extracted oils were quantitatively and qualitatively analyzed to compare the solvents’ performances in terms of kinetics, fatty acid compositions, lipid yields, and classes. Moreover, micronutrients in extracted oils were also respectively quantified by high-performance liquid chromatography (HPLC) and gas chromatography (GC). In addition, the interactions between alternative solvents and rapeseed oil have been theoretically studied with the Hansen solubility methodology to get a better comprehension of dissolving mechanisms. The results indicated that pcymene could be the most promising solvent for n-hexane substitution with higher lipid yield and good selectivity, despite the micronutrient contents were relatively low.

International audience; Solvent extraction processes have been largely used in various industries. They recently were improved through new physical concepts such as CO2 Supercritical Fluid Extraction, Ultrasound assisted process, Microwave-assisted extraction, Instant Controlled Pressure Drop DIC-assisted extraction. . . Systematically, a pretreatment stage of grinding takes place in order to improve the exchange surface increasing the starting accessibility. Swelling of the material structure implies an increase of the porosity thus leading to higher solvent diffusivity within the solid matrix. A new concept of expanded granule powder has recently been defined using Instant Controlled Pressure Drop DIC technology. Whatever the type of solvent is (even CO2-SFE), such a swelled structure dramatically intensifies the kinetics through a higher specific exchange surface thanks to the open pores, while improving the solution solvent–solute diffusivity within the solid. Coupled to ultrasound, the internal transfer of solute within the pore solvent can likewise be intensified by replacing molecular diffusion within the pores by an effective convection transfer. In this work, we carried out a first approach of modeling of solvent extraction kinetics of expanded granules involving higher exchange surface and greater internal diffusion process.

The green extraction has arisen as a new trend in the valorisation of natural resources. As the growing concern on thesafety, health and environment, vegetable oils as alternative solvents have drawn great interests in the green extractionof bioactive compounds from nature plants. Apart from lipophilic carotenoids in this work., compounds with more polarproperties have been initially studied.Firstly, the solubility of major volatile aroma compounds in various vegetable oils was originally investigated through atheoretical modelling of their Hansen solubility parameters, followed by real experimental extractions for verification.Multivariate statistical analyses assisted to classify the solvent power of these oil solvents so as to select the optimal oil.Secondly, the revisit of polar paradox theory inspired us to achieve direct extraction of phenolic compounds usingvegetable oils as solvents. The appropriate addition of surfactants could significantly increase the extraction efficiency.The small angle X-ray scatting helped to further study the effect of surfactants on the supramolecular structure of thevegetable oils. Lastly, the extraction of carotenoids was intensified with the integration of ultrasounds and sunflower oilas the substitute to organic solvents, in which the optimized procedure has been compared with the conventional organicsolvent extraction in terms of procedures, kinetics, yields and environmental impacts., L’éco extraction apparait depuis quelques années comme une nouvelle tendance en matière de technique de valorisation des ressources naturelles. Avec une préoccupation de plus en plus importante concernant la sécurité, la santé mais également l’environnement, l’utilisation d’huiles végétales en tant que solvant alternatifs a été envisagée dans ce travail pour réaliser l’extraction de substances naturelles. Divers composés, avec des propriétés plus ou moins polaires ont été extrait à partir d’une sélection très variée d’huiles végétales.Dans un premier temps, la solubilité de composés aromatiques a été étudiée, de manière originale, grâce à une modélisation théorique des paramètres de solubilités de Hansen. Puis, des études expérimentales ont été réalisées afin de conforter cette approche. Des analyses statistiques permirent d’établir un classement selon le pouvoir solvant de ces derniers, ce qui nous a permis de sélectionner la meilleure huile pour l’extraction des composés aromatiques. Nous nous sommes également inspirés de la théorie du paradoxe polaire, pour réaliser l’extraction de composés phénoliques à l’aide d’huiles végétales. A ce stade, l’addition appropriée de tensioactifs; pourrait permettre d’augmenter significativement l’efficacité de l’extraction des composés cibles ce qui a été analysé de manière plus poussée afin de mettre en évidence l’effet des tensioactifs sur la structure supramoléculaire des huiles végétales. Pour terminer ce travail, l’extraction des caroténoïdes a été intensifiée à l’aide des ultrasons, tout en utilisant l’huile de tournesol comme solvant. Ce procédé optimal a été comparé au procédé conventionnel en termes de temps, de rendement mais également d’impacts environnementaux.

The green extraction has arisen as a new trend in the valorisation of natural resources. As the growing concern on thesafety, health and environment, vegetable oils as alternative solvents have drawn great interests in the green extractionof bioactive compounds from nature plants. Apart from lipophilic carotenoids in this work., compounds with more polarproperties have been initially studied.Firstly, the solubility of major volatile aroma compounds in various vegetable oils was originally investigated through atheoretical modelling of their Hansen solubility parameters, followed by real experimental extractions for verification.Multivariate statistical analyses assisted to classify the solvent power of these oil solvents so as to select the optimal oil.Secondly, the revisit of polar paradox theory inspired us to achieve direct extraction of phenolic compounds usingvegetable oils as solvents. The appropriate addition of surfactants could significantly increase the extraction efficiency.The small angle X-ray scatting helped to further study the effect of surfactants on the supramolecular structure of thevegetable oils. Lastly, the extraction of carotenoids was intensified with the integration of ultrasounds and sunflower oilas the substitute to organic solvents, in which the optimized procedure has been compared with the conventional organicsolvent extraction in terms of procedures, kinetics, yields and environmental impacts., L’éco extraction apparait depuis quelques années comme une nouvelle tendance en matière de technique de valorisation des ressources naturelles. Avec une préoccupation de plus en plus importante concernant la sécurité, la santé mais également l’environnement, l’utilisation d’huiles végétales en tant que solvant alternatifs a été envisagée dans ce travail pour réaliser l’extraction de substances naturelles. Divers composés, avec des propriétés plus ou moins polaires ont été extrait à partir d’une sélection très variée d’huiles végétales.Dans un premier temps, la solubilité de composés aromatiques a été étudiée, de manière originale, grâce à une modélisation théorique des paramètres de solubilités de Hansen. Puis, des études expérimentales ont été réalisées afin de conforter cette approche. Des analyses statistiques permirent d’établir un classement selon le pouvoir solvant de ces derniers, ce qui nous a permis de sélectionner la meilleure huile pour l’extraction des composés aromatiques. Nous nous sommes également inspirés de la théorie du paradoxe polaire, pour réaliser l’extraction de composés phénoliques à l’aide d’huiles végétales. A ce stade, l’addition appropriée de tensioactifs; pourrait permettre d’augmenter significativement l’efficacité de l’extraction des composés cibles ce qui a été analysé de manière plus poussée afin de mettre en évidence l’effet des tensioactifs sur la structure supramoléculaire des huiles végétales. Pour terminer ce travail, l’extraction des caroténoïdes a été intensifiée à l’aide des ultrasons, tout en utilisant l’huile de tournesol comme solvant. Ce procédé optimal a été comparé au procédé conventionnel en termes de temps, de rendement mais également d’impacts environnementaux.

Les huiles essentielles ont une importance economique croissante dans l'industrie des sous-produits d'agrumes. Le procede de flash detente sous vide, un processus provoquant la desintegration de tissus vegetaux, a ete applique a l'extraction d'huiles essentielles des fruits de quatre especes de #Citrus#. Le procede de flash detente (chauffage a la vapeur, puis introduction rapide dans un recipient sous vide) a ete applique a des ecorces de citrons, oranges, mandarines et pomelos. Les huiles essentielles ont ete recuperees a l'aide d'un condenseur, puis separees par centrifugation. Les composes volatils ont ete separes et identifies par chromatographie en phase gazeuse sur colonne capillaire couplee a la spectrometrie de masse. Les rendements en huiles essentielles des ecorces ont ete respectivement de (2,41, 1,43, 0,64 et 0,73) kg x t-1 de fruits pour le citron, l'orange, la mandarine et le pomelo. Les huiles ont ete enrichies en limonene et autres monoterpenes, alors que les concentrations relatives en alcools monoterpeniques (linalol, alpha-terpineol, s-citronellol, nerol, geraniol) et en aldehydes (neral, geranial) ont ete abaissees par rapport aux composes volatils des ecorces brutes. Le procede de flash detente sous vide a permis d'extraire des huiles essentielles de l'ecorce d'agrumes avec des rendements comparables a ceux obtenus par le procede de la Food Machinery Corporation (F.M.C.). Les huiles ont ete enrichies en monoterpenes et correlativement appauvries en composants volatils oxygenes. (Resume d'auteur)

Background Because of the increasingly concern of consumers and public policy about problems for environment and for public health due to chemical pesticides, the search for molecules more safe is currently of great importance. Particularly, plants are able to fight the pathogens as insects, bacteria or fungi; so that plants could represent a valuable source of new molecules. Results It was observed that Medicago truncatula seed flour displayed a strong toxic activity towards the adults of the rice weevil Sitophilus oryzae (Coleoptera), a major pest of stored cereals. The molecule responsible for toxicity was purified, by solvent extraction and HPLC, and identified as a saponin, namely 3-GlcA-28-AraRhaxyl-medicagenate. Saponins are detergents, and the CMC of this molecule was found to be 0.65 mg per mL. Neither the worm Caenorhabditis elegans nor the bacteria E. coli were found to be sensitive to this saponin, but growth of the yeast Saccharomyces cerevisiae was inhibited at concentrations higher than 100 μg per mL. The purified molecule is toxic for the adults of the rice weevils at concentrations down to 100 μg per g of food, but this does not apply to the others insects tested, including the coleopteran Tribolium castaneum and the Sf9 insect cultured cells. Conclusions This specificity for the weevil led us to investigate this saponin potential for pest control and to propose the hypothesis that this saponin has a specific mode of action, rather than acting via its non-specific detergent properties.

La thèse vise l'application du concept de bioraffinerie (extraction, fractionnement, séparation de composés à partir de biomasse avant transformation ultérieure), via le développement d'étapes de production destinées à être associées en un procédé continu. La complexité du solide nécessite une étape de prétraitement effectuée avec une technologie à faible impact environnemental et l'eau subcritique est déjà utilisée comme solvant d'extraction des produits naturels, en sus de leur hydrolyse. Ces travaux ont porté sur l'hydrolyse de polysaccharides (son de riz) et de triacylglycérols (TAG, huile de tournesol) choisis comme modèles. Les caractéristiques de l'eau subcritique (produit ionique, constante diélectrique) mise en oeuvre en réacteurs à circulation construits dans ce but, ont permis l'hydrolyse quasi-totale de l'hémicellulose et des TAG. L'addition de CO2 et donc d'acide carbonique a eu un effet positif sur l'hydrolyse de l'hémicellulose. Les acides gras libres résultant de l'hydrolyse ont été estérifiés en ester éthyliques en présence d'une lipase en réacteur continu en milieu CO2 supercritique, avec un taux de synthèse de 95%. Les cinétiques des réactions ci-dessus d'hydrolyse et d'estérification ont été étudiées. La complexité des interactions entre les nombreux paramètres mis en jeu a conduit à appliquer des méthodes de plans d'expérience. Ces méthodes ont été validées avec succès avec les données expérimentales, montrant ainsi leur utilité dans le développement de procédés. La question importante de la solubilité des extractibles dans l'eau subcritique a été traitée et une méthode de prédiction mise au point et validée avec succès avec les données expérimentales. En conclusion, ce travail montre la possibilité d'appliquer le concept novateur de la Bioraffinerie Intégrée en réacteur continu avec des fluides sub- ou supercritique, contrairement à leur mise en oeuvre actuelle en réacteur fermé, pour la production de composés commercialisables.

Le jasmin, de la famille des Oléacées, est principalement connu pour sonutilisation dans le domaine de la parfumerie.Ces dernières années, de nombreuses recherches ont été effectuées sur cette plante afin de lui découvrir des propriétés médicinales notamment dans le domaine des anticancéreux, des anti-ulcèreux, des antibactériens et des cicatrisants.

The goal of this research is to improve an extractive metallurgy process basedon solvent extraction. This process should fit the exploitation of small localcopper-rich deposits. In these conditions, the plant has to be as compact aspossible in order to be easily transported from one location to a subsequentone. Improved extraction kinetics could ensure a high throughput of theplant despite its compactness. In addition, the extraction reagent shouldnot be damaging for the environnement. On this basis, we propose to useultrasound-assisted solvent extraction. The main idea is to increase theextraction kinetics by forming an emulsion in place of a dispersion thanks tothe intense cavitation produced by ultrasound. The benefit of this methodis to improve the copper extraction kinetics by increasing the interfacialsurface area and decreasing the width of the diffusion layer. We studied theimplementation of an highly branched decanoic acid (known as Versatic-10®acid) as a copper extraction reagent dispersed in kerosene.Emulsification is monitored through the Sauter diameter of the organicphase droplets in aqueous phase. This diameter is measured during pulsedand continuous ultrasound irradiation via a static light scattering technique.The phenomenon of emulsification of our system by ultrasound is effective,and the emulsification process carried out in the pulsed ultrasound mode isat least as efficient as the emulsification obtained under continuous mode.No improvement of emulsification is observed beyond a threshold time ofthe ultrasound impulse. This may be attributed to a competition betweendisruption and coalescence. The use of mechanical stirring combined withpulsed ultrasound allows to control the droplet size distribution.In presence of ultrasound, the extraction kinetics of Versatic-10 acid ismultiplied by a factor ten, and therefore reached a value similar to the kineticsobserved without ultrasound with an industrial extractant such asLIX-860I®(Cognis). Extraction kinetics measurements are carried out bymonitoring the copper ion concentration in the aqueous phase with an electrochemicalcell.We conclude that ultrasound-assisted emulsification can be implementedunder certain conditions. Emulsification is a first step, and the followingdestabilization step has to be studied. The device using ultrasound-assistedemulsification should be followed by an efficient settling-coalescing device. Apossible solution would be to promote emulsion destabilization by increasingthe ionic strength with an addition of MgSO4, a salt that is not extractedby the extraction reagent in the considered range of pH., Doctorat en Sciences de l'ingénieur, info:eu-repo/semantics/nonPublished