Valorisation en synthèse organique d'éco-catalyseurs hétérogènes régénérables à partir de matériaux verts cultivés sur des sols contaminés

The activities of the former metallurgy industries specialized in the production and processing of lead, zinc or other metals have resulted in significant metallic pollution of soils depending on their location. Current studies propose solutions for the requalification of these soils through the phytoremediation processes in order to maximize the value of plants grown on these contaminated soils. This PhD thesis project was thus realized with the aim of valorizing regenerative heterogeneous ecocatalysts. The latter were obtained from the plants cultivated on contaminated soils in organic synthesis for the production of high value added molecules. The contaminated soils used in this project came from the Hauts-de-France region (Auby and Noyelles-Godault). In this light, four types of reactions have been tested to validate the efficiency and recyclability of ecocatalysts:The aminolysis reactionThe Friedel-Crafts reactionThe aza-Michael transformationThe transesterification reactionThe zinc-rich ecocatalysts (EcoZn), obtained from the plant biomass of ryegrass (Lolium perenne L.), were characterized by physicochemical methods and validated their efficiency and recyclability criteria. The latter were successfully used to reach various series of compounds with anti-inflammatory activity known (piroxicam, meloxicam, idrocilamide) and new, inhibitors of farnesyltransferase (for anticancer purpose or to fight orphan diseases such as progeria) or to discover a new aza-Michael acceptor.Les activités des anciennes industries métallurgiques spécialisées dans la production et la transformation de plomb, de zinc ou d’autres métaux ont engendré une pollution métallique importante des sols selon la localisation de ces derniers. Des études actuelles proposent ainsi des solutions de requalification de ces sols via des processus de phytoremédiation afin de valoriser au maximum les plantes cultivées sur ces sols contaminés. Ce projet de thèse a ainsi été réalisé dans le but de valoriser des écocatalyseurs hétérogènes régénérables. Ces derniers sont obtenus à partir des plantes cultivées sur des sols contaminés dans la synthèse organique pour la production de composés à haute valeur ajoutée. Les sols contaminés utilisés dans ce projet proviennent de la région Hauts-de-France (Auby et Noyelles-Godault). Dans cette optique, quatre types de réactions ont été testés pour valider l’efficacité et la recyclabilité des écocatalyseurs :La réaction d’aminolyse,La réaction de Friedel-Crafts,La transformation d’aza-Michael, et enfinLa réaction de transestérificationDes écocatalyseurs riches en zinc (EcoZn), obtenus à partir de la biomasse végétale de ray-grass (Lolium perenne L.), ont été caractérisés par des méthodes physico-chimiques puis validités leurs critères d’efficacité et de recyclabilité. Ceux-ci ont ainsi permis de synthétiser plusieurs séries de composés à activité anti-inflammatoires connus (piroxicam, méloxicam, idrocilamide) et de nouveaux, des inhibiteurs de la farnésyltransférase (à visée anticancéreuse ou pour combattre des maladies orphelines telles que la progéria) ou encore de découvrir un nouvel accepteur d’aza-Michael

Valorization in organic synthesis of heterogeneous eco-catalysts produced from green materials grown on contaminated soils.

Les activités des anciennes industries métallurgiques spécialisées dans la production et la transformation de plomb, de zinc ou d’autres métaux ont engendré une pollution métallique importante des sols selon la localisation de ces derniers. Des études actuelles proposent ainsi des solutions de requalification de ces sols via des processus de phytoremédiation afin de valoriser au maximum les plantes cultivées sur ces sols contaminés. Ce projet de thèse a ainsi été réalisé dans le but de valoriser des écocatalyseurs hétérogènes régénérables. Ces derniers sont obtenus à partir des plantes cultivées sur des sols contaminés dans la synthèse organique pour la production de composés à haute valeur ajoutée. Les sols contaminés utilisés dans ce projet proviennent de la région Hauts-de-France (Auby et Noyelles-Godault). Dans cette optique, quatre types de réactions ont été testés pour valider l’efficacité et la recyclabilité des écocatalyseurs : La réaction d’aminolyse, La réaction de Friedel-Crafts, La transformation d’aza-Michael, et enfin La réaction de transestérificationDes écocatalyseurs riches en zinc (EcoZn), obtenus à partir de la biomasse végétale de ray-grass (Lolium perenne L.), ont été caractérisés par des méthodes physico-chimiques puis validités leurs critères d’efficacité et de recyclabilité. Ceux-ci ont ainsi permis de synthétiser plusieurs séries de composés à activité anti-inflammatoires connus (piroxicam, méloxicam, idrocilamide) et de nouveaux, des inhibiteurs de la farnésyltransférase (à visée anticancéreuse ou pour combattre des maladies orphelines telles que la progéria) ou encore de découvrir un nouvel accepteur d’aza-Michael.The activities of the former metallurgy industries specialized in the production and processing of lead, zinc or other metals have resulted in significant metallic pollution of soils depending on their location. Current studies propose solutions for the requalification of these soils through the phytoremediation processes in order to maximize the value of plants grown on these contaminated soils. This PhD thesis project was thus realized with the aim of valorizing regenerative heterogeneous ecocatalysts. The latter were obtained from the plants cultivated on contaminated soils in organic synthesis for the production of high value added molecules. The contaminated soils used in this project came from the Hauts-de-France region (Auby and Noyelles-Godault). In this light, four types of reactions have been tested to validate the efficiency and recyclability of ecocatalysts: The aminolysis reaction The Friedel-Crafts reaction The aza-Michael transformation The transesterification reactionThe zinc-rich ecocatalysts (EcoZn), obtained from the plant biomass of ryegrass (Lolium perenne L.), were characterized by physicochemical methods and validated their efficiency and recyclability criteria. The latter were successfully used to reach various series of compounds with anti-inflammatory activity known (piroxicam, meloxicam, idrocilamide) and new, inhibitors of farnesyltransferase (for anticancer purpose or to fight orphan diseases such as progeria) or to discover a new aza-Michael acceptor

Ecocatalysis for the synthesis of high-added molecules for therapeutic purposes. Innovative techniques for chemistry and processes

INVInternational audienc

An original approach in green chemistry: From assisted-phytoremediation of contaminated soil to upcycling of plant biomass for biosourced catalyst production

ACTIInternational audienceA kitchen garden soil was sampled in a contaminated urban area located in the north of France. Samples were air-dried and crushed to pass through a 10-mm stainless steel sieve. Due to the high heterogeneity of garden soils in the studied area, much attention have been paid on the homogeneity of soil samples. After this step, the mass of sampled soils (48 kg) was divided to obtain four subsamples Each of them was divided in six replicates, unamended or amended using dicalcium phosphate (DCP) or monocalcium phosphate (MCP) or a mixture of these two compounds (MxP=75%DCP+25%MCP) The phosphorous amendments were added into the soil in small quantity (0.02 %) with the aim at reducing the environmental availability of carcinogenic metals and to increase the Zn availability (Figure 1) After the stabilisation period (2 months) in a greenhouse, 1 5 g of ryegrass seeds (Lolium perenne L.) were sown in the 24 containers. Eight weeks after sowing, ryegrass shoots were harvested, oven-dried at 40 °C and calcined at 500 °C in a muffle furnace (Nabertherm P330, Lilienthal, Germany)

Phytomanagement of contaminated soils by potentially toxic metals in urban areas: A new approach combining sustainable amount of phosphates and ryegrass

ACTNInternational audienc

A sustainable approach to manage metal-contaminated soils a preliminary greenhouse study for the possible production of metal-enriched ryegrass biomass for biosourced catalysts

International audienceTwo kitchen garden soils (A and B) sampled in contaminated areas were amended using phosphates in sustainable quantities in order to reduce the environmental availability of potentially toxic inorganic elements (PTEs) and to favour the availability of alkali, alkali earth and micronutrients. The environmental availability of PTEs was evaluated using a potential plant for revegetation of contaminated soils (ryegrass) and a mixture of low molecular weight organic acids. Despite the highest contamination level of B, the concentration of metals was highest in the ryegrass shoots grown on A for the two harvests. These results correlated well with those obtained using low molecular weight organic acids for Cd, Zn and Cu, whereas this mixture failed to represent the transfer of nutrients due to the presence of biological and physiological mechanisms. The statistical differences between the biomass of ryegrass obtained at the first and the second harvests were attributed to the decrease of available potassium, implicated in the growth and development of plants. Phosphates increased the ratios Zn/Cd, Zn/Pb and Zn/Cu up to 176 ± 48, 38 ± 6 and 80 ± 12, respectively, and made possible the reduction of the concentration of Cd and Pb in the shoots of ryegrass by 22% and 25%, respectively. The concentration of Zn in the shoots of ryegrass from the first and the second harvests grown on soil A were in the range 1050–2000 mg kg−1, making this plant a potential biomass to (i) produce biosourced catalysts for organic chemistry applications in a circular economy concept and (ii) limit human exposure to commercial Lewis acids. A preliminary application was identified. © 2019, Springer Nature Switzerland AG

An innovative and efficient method to synthesize meloxicam in one-step procedure with respect to the green chemistry

International audienceAn improved procedure for the synthesis of meloxicam drug (methyl 4-hydroxy-2-methyl-2H-1,2-benzothiazol-2-amine-3-carboxylate 1,1-dioxide) was described in one-step using mainly impregnated montmorillonite K10 (MK10) with ZnCl 2 as a heterogeneous catalyst. This innovative method was compared to the last described procedure employed in the manufacture of this anti-inflammatory drug by means of some metrics used in a first step of the evaluation process of the environmental impact of a chemical transformation. Apart from the yield, which was 90%, atom economy, waste, environmental factor, reaction mass efficiency and stoichiometric factor were calculated as 91.6%, 8.4%, 0, 8.1% and 1%, respectively. Interpretation of these metrics was given and highlighted the fact that the strategy used in the current study may be considered as an environmental-friendly and sustainable method that fits well in the green chemistry concepts. © 2018, Iranian Chemical Society

Toward a New Way for the Valorization of Miscanthus Biomass Produced on Metal-Contaminated Soils Part 1: Mesocosm and Field Experiments

ACLThe effects of P-fertilizers (mono- and di-calcium phosphates) on the bioavailability of metals and nutrients in leaves and stems of Miscanthus × giganteus were studied in mesocosm and field experiments in order to propose a new way for the valorization of miscanthus biomass. The concentration of potentially toxic elements was generally higher in stems than in leaves. Although P-fertilizers were added to contaminated soils under sustainable conditions (from 0.022% to 0.026% w/w), the average of leaf and stem biomass generally increased in the presence of P-fertilizers due to the changes in the speciation of phosphorus. Leaves of the investigated miscanthus may be of great interest as a catalyst in organic chemistry, since the Ca concentration was up to 9000 mg kg−1 DW. Stems represent a potential biomass that can be used as renewable resource of Lewis acids, currently used in organic syntheses (the sum of Zn, Cu, Mn, Fe, Mg, Si and Al was near 1000 mg kg−1 DW). The percentage of Cd and Pb in leaves and stems of miscanthus did not significantly change with P-fertilizers. Depending on the mesocosm and field experiments, it ranged from 0.004% to 0.016% and from 0.009% and 0.034% for Cd in leaves and stems, respectively, and from 0.004% to 0.015% and from 0.009% and 0.033% for Pb in leaves and stems, respectively

Valorization of new eco-catalysts in the synthesis of anti-inflammatory compounds

International audienc

Valorization of new eco-catalysts in the synthesis of new antitumor compounds

International audienc