Дисертації з теми "Chimie verte et durable"
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Garnier, Estelle. "« Une approche socio-économique de l’orientation des projets de recherche en chimie doublement verte »." Thesis, Reims, 2012. http://www.theses.fr/2012REIME002/document.
Повний текст джерелаSince the last two decades the rise of environmental concerns leads to the sector of chemistry to develop new practices and new products. In particular, new products and processes based on biomass as renewable resources are developed. This is what we call the Doubly Green Chemistry (2GV) (Nieddu et al. 2010).Starting from an initial request for production of "roadmap" and identification of "dominant design" (understood as dominant technological paths) for this new sector from the chemist to guide their research programs, the start idea of this thesis was to test the scheme "exploration / exploitation" of a transition path proposed by the "transition to sustainable management" approach. The main idea it was to test this approach by changing the perspective to deal with this model in terms of representation constructions of the future of this activitie.The work has put forward a variety of representations of the douly green chemistry who settled in the time until the finest level (that of the laboratory). The interest of this result of diversity is that it brings us back to the canonical model that is implicitly built around the transition from a dominant socio-technical regime based on a single artefact to another dominant socio-technical regime based on a another unique artifact.In our case oil and its refinery replaced by biomass and its biorefinery.This result suggests an enrichment of model canonical representation taking into account the possibility of a new socio-technical regime of another nature. Regime whose main characteristic is the need of maintaining a diversity of artifacts
Moutaoukil, Zakaria. "Synthèse et étude de nouveaux agents de flottation et de démétallisation et leurs applications dans l'industrie des phosphates." Electronic Thesis or Diss., Université Côte d'Azur, 2023. http://theses.univ-cotedazur.fr/2023COAZ4027.
Повний текст джерелаNowadays, the mining industry has seen intense activity in the development of reagents and additives for processing a wide variety of minerals, with a special focus on collectors, depressants, as well as chelating agents. Indeed, these agents demonstrated high performances at industrial level, and more particularly in the phosphate industry.The ultimate goal of this thesis work is to develop new “Home Made” reagents and additives in order to support ongoing developments in the phosphate industry in Morocco and to open new perspectives. Accordingly, our research work is focused on the synthesis and performance evaluation of reagents and additives at laboratory, pilot and industrial scales. In this context, agents, belonging to different chemical classes, have been designed for P2O5 low-grade phosphate beneficiation as well as for heavy metals removal. Indeed, with the increase in the world population and the growing demand for free-heavy metals phosphate fertilizers, it is of utmost importance to focus on the exploitation of P2O5 low-grade phosphates and the elimination of heavy metals. In this context, we developed and evaluated various home-made organophosphorus agents during reverse flotation and precipitation processes. These chemicals have proven to be very effective and have produced high yields. Furthermore, during this thesis work, we were also interested in the design, synthesis and evaluation of new bis-phosphonic acids and dihydropyrimidines, with the aim of enhancing and diversifying the portfolio of P-based products, within the framework of green and sustainable chemistry
Drillaud, Nicolas. "Agro-ressources et photo-régulation : vers la synthèse de nouveaux chromophores appliquée au domaine du développement durable." Compiègne, 2012. http://www.theses.fr/2012COMP2050.
Повний текст джерелаThe field of chemistry has witnessed a huge development since the 20th century. Nowadays, this field really needs to become more eco-friendly. One of the major challenges in green chemistry is to replace organic solvents with less hazardous solvents such as water. However, organic compounds are not very soluble in water, which involves a poor yield of organic reactions. To solve this problem, the use of surfactants has been considered. Indeed, those products organized themselves to form micelles, which allows the solubilization of organic compounds and play the part of chimio-reactors. Nevertheless, it can be difficult to extract the products at the end of the reaction, which will make the recycling of the reactional media less efficient. The solution we consider is to synthesize a new surfactant containing an azobenzene as chromophore. Actually, those compounds have the properties to isomerize themselves from their trans forms to their cis forms. This process is reversible. One of these surfactants was synthesized. Its physico-chemicals properties of tensioactivity and photo-regulation have been proved. The use of this surfactant as chimio-reactor for the organic synthesis has been assessed. We were able to show that its employ allows the increase of the yield of the reaction. Moreover, its photochromism properties permit to make the extraction of the products- at the end of the reaction- and also the recycling easier
Schultz, Emilien. "Construire une économie de la recherche sur projets. L’installation de l’Agence Nationale de la Recherche en France et ses conséquences dans les domaines de la génomique végétale et de la chimie durable." Thesis, Paris 4, 2016. http://www.theses.fr/2016PA040106.
Повний текст джерелаThe National Research Agency (ANR) created in 2005 brings the French research system closer to Anglo-saxon ones, where funding agencies play an important part in research policies. Based on an investigation of the ANR and two funding programs in plant genomics and green chemistry, this dissertation shows the significant role played by the ANR in the transformation of funding allocation in France. It contributes both to sociology of science policies and to sociology of organisations. We use data from interviews with researchers, statistical analysis of submitted projects and various reports and media contents. We show that the ANR is an intermediate and semi-autonomous organisation whose aims have significantly evolved since its creation in 2005. The definition of its missions has been a continuous object of struggles which can be seen in the « career » of the agency. Because the ANR mainly « governs through projects », its activities led to the multiplication of competitive calls for projects in France. Some of the consequences are the singularisation of local situations, the scattering of research communities and a change in how researchers behave regarding fundings. More broadly, we show that the multiplication of competitive project funding opportunities leads to an « economy of projectified research ». In this type of economy, the main issue for researchers is to control the way their research is converted into « project » in order to be funded
Tosi, Pierluigi. "Stratégies de valorisation des humines en tant que sous produits de bioraffineries grâce à l’éco conception de matériaux poreux et à leurs applications." Thesis, Université Côte d'Azur (ComUE), 2019. http://www.theses.fr/2019AZUR4100.
Повний текст джерелаDeveloping research and markets around by-products has become indispensable not only from the environmental point of view but also for the circular economy of the industrial processes. In this context, humins constitute one of the most promising by-products. Humins are formed during the biorefinery conversion of lignocellulosic biomass derived sugars into furanic compounds. They consist in a dark-colored, highly viscous, mixture of oligomers derived from random condensations between the several intermediates (mainly HMF and derivatives) formed during the acid catalyzed process. Our group, along with many recent researches, have proven the many hidden possibilities of this furan-rich mixture, which might in turn be attractive for the interesting properties that humins can offer. In this thesis we report several studies performed in order to valorize this material, with a particular focus on humins foams, new polymeric carbon-based porous materials derived from industrial humins in a straightforward and economic attractive way. Humins foams can be prepared by direct heating treatments of humins industrially obtained without any preliminary step such as purification, separation or modification. We show in this manuscript that is possible to control the foams properties (pores dimension, degree of cells opening, morphology, carbon content, etc.) by controlling the preparation parameters such as temperatures applied, heating ramps, gas flow, amount of humins or kind of crucible. The mechanism of foaming has been revealed, several preparation conditions screening carried out, and the material characterized from the chemical, physico-chemical and structural point of view. Furthermore, for the first time, thermal hazard studies for both humins and humins foams have been carried out, which are indispensable for their transport and commercialization in support of entire Biorefinery. Humins foams properties have been deeply studied and tested in several fields, highlighting their most promising applications. Among these, humins foams has been successfully used in the preparation of alumina porous materials by sacrificial templating, which opens the path to future investigations involving further porous materials preparation. Along humins foams, also preliminary studies of crude humins application as dyes for sensitized solar cells and for further materials and composites preparations were carried out. This thesis not only proves how promising humins materials are, highlighting their major advantages and the points of s trength that would be competitive on the market, but also aims to increase the interest around these materials. This thesis offers a good starting point for further and future valorizations, with advantages that will involve the environment along with the entire Biorefinery
Mangin, Floriane. "Synthèses de nouveaux tensioactifs éco-compatibles : étude de synthèses catalytiques et radicalaires en milieu micellaire." Thesis, Compiègne, 2015. http://www.theses.fr/2015COMP2224/document.
Повний текст джерелаBased on concepts of sustainable development and green chemistry, one of the alternatives envisioned by chemists is to substitute organic solvents, which can be dangerous and toxic, for greener solvents. Water is the best candidate for this substitution because it is thesafest and cheapest solvent in our countries : this solvent is non-toxic, non-flammable and inexplosive. In order to overcome the low solubility of most of organic compounds in water, surfactants can be used to improve the reaction yields. Media thus obtained are difficult to recycle because they require high dilution in order to break aggregates and recover products. Therefore, using photo-switchable surfactants is a good alternative because they can organize/disorganize by light irradiation. Organic compounds could be recovered after reactions and the recyclability of the medium can be improved. For this purpose, we synthesized three surfactants having an azobenzene moiety (anionic,cationic, nonionic), to test them in micellar catalysis. Some of these surfactants, after determining their physicochemical properties (CMCs and UV-visible spectra) were studied in a pallado-catalyzed reaction, the allylic substitution of Tsuji-Trost. We have successfully demonstrated the value of using a photo-switchable surfactant compared to commercialones in terms of yields and recyclability. In other hand, Barton decarboxylation, described for the first time in 1983, permits the formation of alkanes from carboxylic acids, using tin derivatives as hydrogen donors. Since then, this reaction has always been used as a key step in total synthesis of natural compounds in organic solvents. In addition, historically, this reaction was carried out by conventional activation (heat or ultraviolet light). Therefore, we decided to study this radical decarboxylation in water, in the presence of surfactants and using unconventional activation modes : microwave and ultrasound. Moreover, instead of tin, we preferred the use of N-phenylmaleimide, already known and studied as a radical trap, to obtain maleimides substituted by carbon chains. Yields obtained in micellar media were found tobe at least as good as in organic solvents
Gicquiaud, Julien. "Activation électrophile des alcynes vis-à-vis de l'attaque de nucléophiles carbonés catalysée par les acides de Bronsted : éco-conception et analyse du cycle de vie d'une nouvelle voie catalytique." Thesis, Bordeaux, 2019. http://www.theses.fr/2019BORD0446.
Повний текст джерелаThis manuscript presents a study of cycloisomerization reactions, in accordance with the principles of green chemistry, based on the electrophilic activation of alkynes in the presence of achiral and chiral Brønsted acids via the formation of vinyl cation intermediates and the attack of the latter by carbon nucleophiles. The use of a catalytic amount of Brønsted acid with 2-alkynylbiaryl substrates delivered phenanthrene derivatives in good to excellent yields under mild reaction conditions. High catalytic activities, along with differences of chemo- and regioselectivity were observed when comparing to carbophilic metallic Lewis acid catalysts.The use of a directing group substituting the alkyne function, the 2-naphtholyle moiety, resulted in increased basicity of the alkyne, increased regioselectivity of the protonation step and the creation of hydrogen bonding with the catalyst, paving the way for the development of an asymmetric version of cycloisomerization reactions. In the presence of chiral Brønsted acids, such as N-triflylphosphoramides, the enantioselective synthesis of atropisomeric phenanthrenes was achieved with excellent yields and good enantiomeric excesses. An intermolecular reaction of hydroarylation of alkynes in the presence of the same catalysts delivered atropisomeric alkenes in excellent yields and enantioselectivities.The use of a directing group on the alkyne also allowed for the first time the development of Brønsted acid-catalyzed enyne cycloisomerization reactions involving the initial, selective protonation of the alkyne function. A variety of polycyclic scaffolds were obtained by this methodology with high yields and moderate enantioselectivities.The cycloisomerization catalytic reaction is known to chemists as a model reaction respecting several principles of green chemistry such as atomic economy, waste limitation and the principle of catalysis.However, no quantitative evidence is provided by chemists to promote the sustainability of the methodologies developed in their laboratories. Several monocriteria parameters and multi-criteria methods have been developed to try to address this environmental quantification issue. However, the interest in developing new catalytic systems should be associated with the development of more environmentally efficient processes in addition to knowing if it is more chemically efficient.Life cycle assessment (LCA) is the standardized reference method for quantifying the environmental impacts (e. g. climate change, toxicity, resource use) of a product over its life cycle. LCA has already been applied to green chemistry developments to compare the durability of chemical reactions, or for eco-design applications. However, it is not trivial to use LCA at the laboratory scale because it requires (i) data that are difficult for the chemist to access (ii) additional modeling steps to estimate potential impacts at the industrial scale (iii) requires the expertise of a LCA practitioner. [...]
Bruniaux, Sophie. "Nouveaux hydrotropes biosourcés : conception, synthèse et propriétés physico-chimiques en milieu hautement salin." Thesis, Compiègne, 2017. http://www.theses.fr/2017COMP2378.
Повний текст джерелаHistorically, chemical industry was based on fossil ressources, but alternative processes have been developed since the nineteens to be green and to answer to the environmental eco-responsibility questions. In this context, a collaboration work between three public laboratories and the SAS PIVERT emerged to find new biosourced hydrotropes starting from various polyols – such as glycerol, main byproduct of the fuel production – and resistant to high saline conditions. A specific design was defined by our physico-chemical partner for the synthesis of hydrotropes. Differents approaches were used to obtain these compounds, such as a new method of methylation using sub/supercritical methanol with a phase of optimization, and another about the scope of the reaction that reduced the reaction steps. The transposition of the reductive alkylation of various alcohols was also realized – using a heterogeneous catalysis – with the obtention of various ethers, in continuous flow conditions, by the intermediate of the use of the HCube Pro from ThalesNano
Tremblay-Morin, Jean-Philippe. "Porphyrines cationiques romées pour la radiothérapie et chimie verte catalysée." Mémoire, Université de Sherbrooke, 2005. http://savoirs.usherbrooke.ca/handle/11143/3864.
Повний текст джерелаTremblay-Morin, Jean-Philippe. "Porphyrines cationiques romées pour la radiothérapie et chimie verte catalysée /." [S.l. : s.n.], 2005.
Знайти повний текст джерелаPoupon, Roland. "L'Alter-révolution verte thailandaise : aviculture et riziculture conventionnelle et alternative dans une perspective de développement durable." Toulouse 2, 2009. http://www.theses.fr/2009TOU20010.
Повний текст джерелаThis thesis aims at analyzing the agricultural revolutions in Thailand. The method used was a study of the downstream channels’ agents through interviews, surveys and price observations, on value chain, convention and network theoretical basis. Research compared rice growing and poultry farming in both Khorat and Suphan Buri provinces. The first part of the thesis shows that the State initially curbed the revolutions’ penetration, but thereafter reversely contributed to modernization. Today, its policy is evolving towards decentralization, support to SMEs and to peasants. The second part focuses on the deployment of revolutions, dependent on new technologies developments, which led to intensification, differentiation and specialization, hence to the arrival of standardized conventional products on the market. As a consequence, agricultural sectors concentrated on specific territories, while territories specialized in specific sectors. Nevertheless, for environmental and social reasons, some forms of traditional agriculture survived, like fragrant rice or native chicken, and became alternatives to agricultural revolutions: biological, ethical or spiritual agricultures, they were baptized “Alter-Green Revolution”. The third part explains this resilience by the influence of demand, quality and logistics. Identity quests also impact the channels. Green and Alter-Green Revolutions are interdependent and related through multiple networks (NGO, Sino-Thais, Sogo Shosha) with multiple links. These interrelationships build an “alternative tree”, source of innovation and security for the actors, which become impossible to isolate from each other
Ngo, Biboum Bimbong Rosa. "Polyoxométallates et chimie verte : molécules et matériaux nanostructurés pour la conversion de l'énergie et l'environnement." Phd thesis, Université Paris Sud - Paris XI, 2011. http://tel.archives-ouvertes.fr/tel-00612028.
Повний текст джерелаNgo, Biboum Bimbong Rosa. "Polyoxométallates et chimie verte : molécules et matériaux nanostructurés pour la conversion de l’énergie et l’environnement." Thesis, Paris 11, 2011. http://www.theses.fr/2011PA112095/document.
Повний текст джерелаThis thesis focuses on the synthesis of nanostructured composite materials based on polyoxometalates for energy conversion and applications to environmental problems. To achieve these goals, many new compounds of this family of molecular oxides were synthesized and were associated with different nature friendly matrices, in agreement with the main criteria of Green Chemistry. In the field of energy, the new catalysts have proved very effective in important but difficult to achieve reactions, such as producing hydrogen, oxygen reduction or water oxidation. Similarly, among applications to pollution problems, these nanomaterials have shown a strong electrocatalytic and photocatalytic activity for the reduction of nitrogen oxides, bromate and for the photodegradation of a toxic textile dye, Acid Orange 7. The performances of these new catalysts are comparable to those of the best known systems
Maza, Lisa Jésus. "Résines vertes à base de lignine organosolve." Thesis, Pau, 2017. http://www.theses.fr/2017PAUU3039.
Повний текст джерелаPhenolic resins, may be used in the wood industry for the manufacture of particle boards or plywood, after gluing, impregnation and/or hot-pressing steps. They are mainly obtained by step polymerization (polycondensation) from formaldehyde and phenol. These two raw materials are currently petrochemicals.This thesis work, supported by Rolkem, a company specialized in the design and manufacture of resol type phenolic resins, aims to reduce the use of non-biobased materials by replacing phenol with lignin exhibiting a phenolic structure and a structural similarity with the network of phenolic resins. Lignin is abundant in the environment and easily available. To achieve the industrialization of these new biobased resins, a study on the understanding of the reaction mechanisms has been carried out to favor the incorporation of lignin within the resins. It has been possible to replace up to 50wt.% of the phenol with organosolve lignin and to reduce the initial concentration of formaldehyde at the same time. 75wt.% substitution has been achieved using a Kraft lignin by reducing up to 30wt.% of the formaldehyde concentration as compared to conventional resins. The new biobased resins respect the Rolkem specifications. Thanks to this work results, the scale transfer of biobased resins from the laboratory scale to the industrial pilot was possible, while respecting industrial constraints such as productivity, quality, safety and environment. In addition, the industrial plywood bonding tests were in accordance with the prerequisite.In addition to the above objectives the reactivity of BiolignineTM with formaldehyde has been studied under conventional heating and microwave irradiation. This complementary study allows the correlation of the lignine-formaldehyde reactivity and the heating modes to specifically reach products resulting from addition or condensation reactions
Martinez, Victor. "Utilisation conjugée de complexes du fer et du ruthénium pour la chimie verte : formation stœchiométrique et catalytique de liaisons carbone-carbone et carbone-azote." Bordeaux 1, 2003. http://www.theses.fr/2003BOR12704.
Повний текст джерелаHuet, Marion. "Valorisation hydrothermales de la liqueur noire à des fins énergétiques et de chimie verte." Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAI085/document.
Повний текст джерелаThis thesis aims to study sulfur free black liquor valorization through two hydrothermal processes: supercritical water gasification and hydrothermal liquefaction. These processes will be compared to the industrial process (evaporation and Tomlinson boiler) with 3 mains criteria: energetic yield, sodium recovery and phenolic molecules production.In supercritical conditions, gas formation is competitive with char formation. Fast heating and high temperature permit to increase gas yield, thus energetic yield. However, conversion of phenolic compounds from lignin is low below 500°C, leading to a lower energetic yield than reference. In a continuous process, at high temperatures (700°C) and fast heating, energetic yield should be 2 times higher than industrial process (simulation at thermodynamic equilibrium). Wood prehydrolysis and softwood lead to a lower conversion of black liquor.Hydrothermal liquefaction produces a biocrude which can be burnt and phenolic platform compounds. Indeed, lignin is depolymerized into reactive fragments which can be degraded into platform phenolic molecules. Moreover, the recombination of these fragments, leading to biocrude formation, is favored by the carbohydrates derivatives in black liquor. Wood prehydrolysis and hardwood lead to better energetic and phenolic molecules yields.Sodium recovery is satisfactory for both processes. Substitution of Tomlinson recovery by a hydrothermal process is then possible
Beillard, Audrey. "Préparation par mécanochimie de complexes NHC-métal et application en catalyse." Thesis, Montpellier, 2017. http://www.theses.fr/2017MONTT172.
Повний текст джерелаDue to the constant increase of publications reporting new organometallic complexes, it becomes urgent to develop alternative synthetic methods to the classical ones that use toxic solvents, high reaction temperatures and that do not always lead to the desired complexes in good yields. The use of ball-mills for the synthesis of NHC-metal complexes (silver and copper in particular) and their precursors has enabled the development of efficient, general, quick and more sustainable methods. These methods give an access to interesting compounds, difficult to synthesize using another pathway. Numerous complexes never reported in the literature were also formed. These complexes have demonstrated their efficiency as catalysts in the A3 reaction to form the propargylamines
Aissa, Rabha. "Coprécipitation d'ions FeII et FeIII par Na2CO3 en milieu sulfaté et synthèse de la rouille verte substituée aluminium." Nancy 1, 2004. http://www.theses.fr/2004NAN10154.
Повний текст джерелаFormation of sulphated green rust {RV2(SO42-)} is preceded by precipitation of a sulphated ferric basic salt and a badly crystallized ferric oxyhydroxyde. The study of the substitution of the FeIII cations by the AlIII cations in the structure of RV2(SO42-) shows that it is necessary to introduce an excess of FeII ions in solution as required for the stoichiometry of the green rust to obtain a single phase aluminium substituted sulphated green rust. This new compound is characterized by a crystal size of about 50 nm and the Mössbauer spectrum is characterised additional ferrous doublet. The coprecipitation of the FeII ions and FeIII in sulphated medium by the weak Na2CO3 was studied. Green rusts then obtained are unstable and require immediate analysis after synthesis. This transformation is inhibited by the presence of silicate anions in the reaction medium which react with the surface of green rusts thus preventing their dissolution. The transformation of the RV2(SO42-) in RV1(CO32-) is carried out by exchange of anions
Quintin, François. "Synthèse de complexes organométalliques par mécanochimie. Catalyse, photochimie et activités biologiques." Thesis, Montpellier, 2020. http://www.theses.fr/2020MONTS026.
Повний текст джерелаKnown for their activities in catalysis and biology, organometallics complexes are an important part of current chemistry. However, their syntheses are still complicated from an experimental and environmental point of view (low yields, use of toxic solvents, …) and it becomes urgent to develop sustainable alternative synthetic methods. This thesis builds on mechanochemistry as an efficient alternative for the synthesis of organometallics complexes. Firstly, new silver(I) and ruthenium(II) complexes featuring NHC ligands were synthesized by mechanochemistry. These complexes were then evaluated in catalysis (hydrogen transfer reaction and ring-opening metathesis polymerization) and tested for their antitumoral activity. A second family of ruthenium(II) and iridium(III) complexes were synthesized by ball-milling, and tested in photoredox catalysis by mechanochemistry. During these different reactions, an improvement of experimental (shorter reaction time, use of optimal quantities of reactants) and environmental conditions (absence of toxic solvent) was observed, in addition to high yields
Jean, Marc Alexandre. "Développement d'une méthode verte pour la construction des γ-hydroxybuténolides et synthèse de produits naturels et d'une nouvelle classe de peptidomimétiques". Doctoral thesis, Université Laval, 2017. http://hdl.handle.net/20.500.11794/31594.
Повний текст джерелаThe work accomplished concerns primarily the total synthesis of biologically important organic molecules including secondary metabolites and non-natural compounds. Importantly, this research also led to the discovery and development of new methodology for the synthesis of oxygen heterocycles. First, a concise, biomimetic route to paracaseolide A is described. This complex molecule was synthesized in 4 or 5 steps via akolactone A, a natural product itself that is assumed to be an intermediate in the biosynthesis of paracaseolide A. Key steps include (i) regiocontrolled aldol reaction of α–angelica lactone with myristyl aldehyde, (ii) oxyfunctionalization of a 2-silyloxyfuran to generate an (E)–α–alkylidene–γ–hydroxy butenolide, and (iii) Diels-Alder dimerization of the latter and in situ cyclodehydration to provide paracaseolide A. The stereochemical outcome of the Diels-Alder cycloaddition is discussed. In addition, the synthesis allowed the discovery of three unprecedented transformations, notably the conversion of α–alkylidenebutenolides to γ–hydroxybutenolides and 2-silyloxyfurans, and the aerobic oxidation of the latter. In particular, a new, green and practical method was developed for converting 2-silyloxyfurans to γ–hydroxybutenolides using oxygen as oxidant. A mechanism for this autoxidation is proposed, supported by control experiments and the isolation of side products. The utility of this method was demonstrated by a short synthesis of isofugomycin (5 steps, 35% overall yield). Following on from our interest in polycyclic terpenoids, and more precisely the labdane family, we developed a unified route to three structurally novel secondary metabolites, namely, amomaxin A and B and ottensidione. These molecules contain a nine-membered carbocycle which is rarely encountered in Nature. All three targets were assembled from a common precursor, obtained in 16 steps from (+) - sclareolide. The route entailed judicious application of several important reactions, including Grob/Wharton fragmentation and ring closing metathesis (RCM). The synthesis enabled establishment of the correct stereochemistry of amomaxin A, which was misassigned in the original publication. In a related project, we corrected the structure of a new labdane natural product, independently isolated from two Alpinia plants by different research groups, by careful analysis of the reported spectroscopic data and NMR comparison of the chemical shifts with those of ottensinin. vi Finally, we developed a diversity - oriented synthesis of non - symmetric, diol - based peptidomimetics as potential protease inhibitors of human immunodeficiency virus (HIV). The route begins from a readily available carbohydrate building - block and makes use of conjugated addition as a key step. It allows divergence at four distinct points, thereby generating a library of new, drug-like compounds for biological screening.
Voyé, Pierre. "Valeur verte et approches spatialisées de la maîtrise de la demande d’énergie." Thesis, Bourgogne Franche-Comté, 2019. http://www.theses.fr/2019UBFCG007.
Повний текст джерелаThe current environmental and economic context implies a need to manage energy demand. In order to do this, understanding completely the determinants of energy demand is first required. Also, there is a need to find tools to reduce energy consumption. In this thesis, we are interested in the consequences of a household’s choice of location on energy consumption and on the role of the green value to promote the adoption of energy-efficient buildings by households. The first chapter analyzes an urban microeconomic model of residential choice of location and energy consumption. In order to complete this theoretical analysis, we estimate the energy demand of the residential sector. The second and third chapters study the green value and its role in the promotion of green buildings. In chapter 2, we present a meta-analysis of the literature estimating the green value. In chapter 3, we use a spatial hedonic model to estimate the residential green value for the urban area of Dijon. Finally, in the last chapter, we study the residential choice of households concerning the energy performance of their dwelling. To do so, we estimate the probability of households to live in an energy-efficient building or not. The results of these estimates and the results of the previous chapters are then mobilized to discuss the efficiency of the public policy used for managing energy demand
Castries, Augustin de. "Synthèse de dérivés du cyclam et applications de leurs complexes métalliques dans des procédés catalytiques de chimie verte." Versailles-St Quentin en Yvelines, 2007. http://www.theses.fr/2007VERS0013.
Повний текст джерелаThis work has been devoted to the synthesis of various macrocycles derived from cyclam bearing sulfinyl and sulfonyl pendant arms and to the study of their potential applications in catalysis. The first part describes the synthesis of perfluorinated macrocycles by Michael addition on various perfluorinated acceptors. The catalytic activity of the corresponding complexes has been studied in autoxidation under fluorous biphasic conditions. The second part describes the synthesis of macrocycles from arylvinylsulfoxides and sulfones. The auxiliary role of the sulfinyl and sulfonyl moieties in the complexation of metallic cations Cu2+ and Eu3+ has been studied. The catalytic activity of the Cu (II) complexes and their ligands has been evaluated in catalytic reactions of Michael additions and ring opening of epoxides in aqueous and organic medium. The third part is devoted to the development of solid phase synthesis for the preparation of trifunctionnalized cyclams
Guo, Jia. "Elaboration de matériaux biodégradables et biocompatibles par de nouveaux procédés catalytiques respectant les principes de la chimie verte." Paris 6, 2013. http://www.theses.fr/2013PA066819.
Повний текст джерелаLachguar, Abdelhak. "Pour une chimie plus verte - catalyseurs chiraux supportés sur solide pour recyclage et développement de procédés en continu." Thesis, Toulouse 3, 2022. http://www.theses.fr/2022TOU30023.
Повний текст джерелаThe awareness by society of the concept of sustainable development has led chemists to rethink all industrial processes through the twelve principles of green chemistry. In this “green” approach to chemistry, catalysis, in particular with transition metal complexes, occupies a key place: improvement of activities (lower energy consumption), improvement of selectivities (fewer by-products), discovery of new catalytic reactions (less dangerous reagents, clean solvents, economy of atoms, etc.), control of stereochemistry (synthesis of drugs, polymers) ... Unfortunately, the sometimes high cost of catalysts, their difficulties in recovery or recycling is a barrier to their industrial use. The heterogenization of catalysis reactions (catalyst recycling, simplified product purification) and the development of continuous processes are major challenges that meet societal (environment) and industrial expectations. We wish to answer it here by relying on catalysts prepared from chiral phosphine, phosphinocarbene and ferrocenic carbenes (planar and central chirality) ligands synthesized in the team and having demonstrated excellent activities and selectivities in asymmetric catalysis (hydrogenation, Suzuki -Miyaura). These ligands will be functionalized in order to allow their grafting on a solid support. The nature of the supports (spherical silica, mesoporous silica, etc.), the grafting sites (on the surface, in pores or channels) are elements that we wish to study in order to better understand the role of surface interactions and the phenomena of confinement on the activity and enantioselectivity of the supported catalysts
Kutudila, Pricilia. "Structure et réactivité des triarylbismuths : approche théorique et expérimentale." Thesis, Paris Est, 2017. http://www.theses.fr/2017PESC1123/document.
Повний текст джерелаTriarylbismuths are organometallic reagents of growing interest for organic synthesis, for their ability to transfer the three aryl moieties in C-C Pd-catalysed cross-coupling reactions. These essentially non-toxic, atom efficient reactants are attractive in the context of environment-friendly chemistry and have applications in pharmaceutical chemistry and in material science. However, their development is hampered by lack of theoretical understanding. This thesis aims to explore the reactivity of these species by comparing the experimental data to fundamental theoretical studies (structural, spectroscopic, thermodynamic and kinetic properties) resulting from DFT calculations. The ultimate goal is to predict new reactivities and selectivities. A first approach consists in a comparative study on the relation between structure and properties in compounds having a pnictogen central atom like bismuth, and in different organobismuths. The existing experimental data (crystallographic, NMR, IR) were compared to the results of theoretical calculations (structures, energies, vibrational modes, reactivity parameters, etc.). After highlighting the intrinsic properties of these compounds and validating the DFT method, a new study was undertaken to elucidate the relations between structure and reactivity. This second investigation enabled us to validate the mechanism of the cross-coupling reaction involving triarylbismuths under palladium catalysis. The three major steps of the catalytic cycle have been examined, i.e. the oxidative addition, transmetallation and reductive elimination, and validated by characterizing the different intermediates and transition states. The second transmetalation step involving the triarylbismuths has also been deeply investigated. The transferability of the three aryl groups and the influence of the electronic and steric effects of the substituents on the energy barrier have been evaluated. Finally, the reactivity of triarylbismuths has been compared with that of other organometallics, to develop new synthetic approaches
Estager, Julien. "Méthodes d'activation non conventionnelles et solvants propres pour une chimie durable : synthèse et valorisation organique des liquides ioniques." Chambéry, 2007. http://www.theses.fr/2007CHAMS048.
Повний текст джерелаThese last years, RTILs have become a very attractive alternative to conventional solvents. Because of their negligible vapor pressure, they are used as green solvents. In addition, their wide liquid range, tunable polarity or good solvating ability make them very interesting in organic synthesis. Finally, their non flammability and non explosive character make them good candidates to replace traditional molecular solvents in term of green chemistry. The objectives of this PhD thesis are the synthesis and the valuable use of these compounds by taking advantage of some of their remarkable properties with the use of non conventional activation methods such as microwave and / or ultrasound irradiation. The nature and properties of ionic liquids are described along the first chapter of this work and then the physical effects that lead to sonochemistry and chemistry effects under microwave irradiation are also discussed. The second chapter of this thesis described the advantage of non traditional activation methods for improving the synthesis of second generation ionic liquids. By using, ultrasonic irradiation, different families of nitrogen-bearing ionic liquids are obtained in a solvent-free or in aqueous medium, which gives a greener touch to the overall process. Aiming to overcome some limitations of this method, a new activation method using simultaneous ultrasound/microwave irradiation has been shown to lead to good yields in second generation ionic liquid in a kinetic of only few minutes. Then, the synthesis of benzion via benzoin condensation reaction has been studied with various ionic liquids as catalysts. Microwave activation and ultrasonic irradiation have been tested and good yields in benzoin have been observed whereas the recycling of the ionic catalyst was shown to be possible in specific conditions. Finally, different ionic liquids have been chosen to catalyse the electrophilic cyclisation of Pictet-Spengler, a classical synthetic method to reach bioactive molecules. Various acidic ionic compounds, including task specific ionic liquids have been tested and good conversion in tetrahydro-β-carbolines have been obtained with the most suited ionic catalyst
Farhat, Asma. "Vapo-diffusion assistée par micro-ondes : conception, optimisation et application." Phd thesis, Université d'Avignon, 2010. http://tel.archives-ouvertes.fr/tel-00547809.
Повний текст джерелаLangumier, Mikaël. "Biodétérioration des structures portuaires en acier : synergie entre la physico-chimie du fer en milieu marin et les micro-organismes sulfurogènes." Phd thesis, Université de La Rochelle, 2011. http://tel.archives-ouvertes.fr/tel-00717856.
Повний текст джерелаMissaoui, Rafik. "Extraction verte et caractérisation des molécules bioactives dans les coproduits de la production d'asperge (Asparagus officinalis L.)." Master's thesis, Université Laval, 2018. http://hdl.handle.net/20.500.11794/31327.
Повний текст джерелаPlants belonging to the family of Asparagaceae, especially asparagus (Asparagus officinalis L.) contain a wide range of bioactive molecules such as polyphenols, flavonoids and saponins. These compounds have several health properties: antioxidant, anticancer and cardioprotective effects. In addition to that asparagus production generates a significant amounts of co-products, making it a good choice for the valorisation through the production of bioactive extracts for the functional food market. In this study, carried out with a green biorefinery view, we used only ethanol and water under optimum conditions rather than other solvents sometimes adopted in extraction of bioactive molecules and which may be harmful for human health. Total polyphenol and flavonoid were determined in different segments of the asparagus stem (upper and lower parts), differents varieties of asparagus and co-products of the Guelph Millenium variety. Identification of polyphenols was performed by UPLC-MS/MS and quantification of saponins was performed by a spectrophotometric method. The optimization of the extraction of polyphenols and flavonoids was accomplished by modulating the temperature, the ethanol concentration and the solute/solvent ratio. The polyphenols present in asparagus are especially flavonoids and phenolic acids with a dominance for rutin (92%) .The polyphenols have been found to be more concentrated in the upper part of the asparagus stem (1.15 %) and represent 0.6 % for the basal parts of the stem and 1.4 % for the lower grade asparagus based on dry matter. The optimized extraction parameters are 80 % ethanol at 70 °C for 3 hours with a solute/solvent ratio of 1:40. This study is not limited to protect the environment by removing asparagus co-products from landfills, but adds values to these co-products. Key words : Asparagus, co-products, optimization, polyphenols, flavonoids, saponins, UPLC-MS/MS.
Schneider, Yoann. "Utilisation des diazirines comme source d'azote électrophile pour la synthèse d'hydrazines et d'hétérocycles." Thèse, Université de Sherbrooke, 2016. http://hdl.handle.net/11143/8736.
Повний текст джерелаBandres, Matthieu. "Synthèse de solvants et plastifiants d’origine naturelle selon une démarche d’éco-conception : application à la formulation de vernis à ongles." Phd thesis, Toulouse, INPT, 2007. http://oatao.univ-toulouse.fr/7119/1/bandres.pdf.
Повний текст джерелаNun, Pierrick. "Micro-ondes et activation mécanique : applications en synthèse organique et peptidique." Montpellier 2, 2009. http://www.theses.fr/2009MON20107.
Повний текст джерелаGreen or Sustainable chemistry has become a growing area in the last few years. The necessity to limit the impact of human activities on environment and health, to find new resources for reactants and solvents drives us to develop a new way to perform chemistry. For this purpose, we have chosen to work on the development of new methods allowing us to perform solvent-free reactions. Among all these methods, mechanical and microwaves activations were specifically studied. Using microwaves, we first developed solvent-free Petasis reactions, giving a large variety of tricycles in one step and with a basic aqueous wash as the only purification step. We also showed that the Suzuki coupling could be performed in 10 min at 110°C without any solid support such as alumina and using a new NHC-Pd catalyst, the PEPPSI. Using mechanical activation, the interest of this method for the synthesis of nitrones and hydrazones was proven, the compounds were obtained after condensation of an amine on a carbonyle. Hydrazones could also be N-alkylated in a second step in basic conditions. The applicability of mechanical activation to prepare di- and tri-peptides using activated aminoacids, Urethane N-carboxyanhydrides (UNCA), was also shown. Peptides were obtained after ball-milling a UNCA with an aminoester chlorhydrate in basic conditions. Finally, one of the first applications of a ball-mill in asymmetric synthesis was realized, in order to prepare aminoacids after alkylation of Schiff bases in presence of cinchonidinium salts
Chatel, Grégory. "Liquides ioniques et ultrasons pour l'époxydation d'oléfines : combinaison synergique plus éco-compatible." Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00780336.
Повний текст джерелаLosfeld, Guillaume. "L’association de la phytoextraction et de l’écocatalyse : un nouveau concept de chimie verte, une opportunité pour la remédiation de sites miniers." Thesis, Montpellier 2, 2014. http://www.theses.fr/2014MON20193.
Повний текст джерелаIncreasing pressure on mineral resources has drawn research efforts into innovative supply and recycling. Metal-rich biomass produced in phytoextraction proved an interesting starting-material for Green Chemistry. It allows the production of new catalysts, referred to as ‘ecocatalysts'. They provide the following benefits: access to new molecules, increased yields in chemicals production, increased regio- and chemo-selectivity… This results in potentially high added-value and possible development of a new economic outlet. This new approach to using metal-rich biomass could spur the development of phytoextraction, a technique considered promising for long, yet without credible economic applications. In this regard metallophyte biodiversity hotspots, such as New Caledonia are of particular interest to assess biomass supply. Ambitious and costly ecological restoration of the mining environment in New Caledonia is increasingly questioned. The development of phytoextraction on most degraded areas, e.g. quarries and wastes piles, to produce biomass for Ecocatalysis could provide revenues, while ensuring reclamation. This thesis looks into a possible outlet in New Caledonia, from plants to catalysts and final chemical products
Hallot, Gauthier. "Synthèse, caractérisations et vectorisation des nanoparticules de bismuth métallique pour des applications théranostiques." Thesis, Sorbonne université, 2019. https://accesdistant.sorbonne-universite.fr/login?url=http://theses-intra.upmc.fr/modules/resources/download/theses/2019SORUS272.pdf.
Повний текст джерелаMetallic bismuth nanoparticles are poorly described in the literature and yet they have a high medical potential. Their utility is particularly described in therapeutic and/or diagnostic applications. In addition, bismuth is an abundant, inexpensive and biocompatible element. In this project, a robust and reproducible synthesis of metallic bismuth nanoparticles in water in a non-continuous process was developed by applying the principles of green nanochemistry. This synthesis was then transferred to a continuous process to increase the productivity of obtaining nanoparticles. The characterization of their surface, chemical and colloidal stability as well as their cytotoxicity were studied in order to consider their use in biological environments. Three types of hydrophilic, hydrophobic and fluorophilic nanoparticles have been obtained. Hydrophilic nanoparticles with polyethylene glycol on their surface are stable for 24 hours in saline solution. Hydrophobic nanoparticles have been incorporated into oil-in-water emulsions. On the other hand, polyfluorinated nanoparticles containing insufficient fluorine on the coating agent could not be incorporated into a fluorinated oil. Finally, a preliminary study did not show a radiosensitization effect of bismuth nanoparticles. In vitro and in vivo studies of these nanoparticles are planned to definitively conclude on their radiosensitizing effect
Oddon, Frédéric. "Les oxygénases artificielles : nouveaux outils pour la catalyse asymétrique d'oxydation d'alcènes et de thioéthers dans le cadre de la “chimie verte”." Phd thesis, Grenoble, 2010. http://tel.archives-ouvertes.fr/tel-00558081.
Повний текст джерелаGarel, Claire. "De la phytoextraction en Nouvelle-Calédonie aux Eco-Mn : étude structurale de catalyseurs biosourcés et innovants." Thesis, Montpellier, 2017. http://www.theses.fr/2017MONTT185.
Повний текст джерелаMineral resources are running out, ores are hardly accessible, and ores processing damage the environment. In New-Caledonia, nickel ores mining requires to remove all the upper layers of the ground, leading to open-cast mines subjected to erosion, which threaten the environment and the biodiversity of the archipelago. Although mining ores exploitation is important for the economy of New-Caledonia, the ecological remediation of mining areas through the restoration of a vegetation cover, are necessary.ChimEco laboratory has demonstrated that it is possible to reintroduce pioneering endemic plant species, which are resistant to climate conditions and accumulate manganese, to restore New-Caledonian mining sites. These accumulating plants extract Mn from the ground to their aerial parts: it is called phytoextraction. Besides, ChimEco laboratory puts forward a new scientific and economic valorisation of phytoremediation efforts in New-Caledonia. Indeed, an innovative process has been developed to recycle metallic elements from manganese enriched biomass into innovative and polymetallic catalysts for organic synthesis. This new process is called Ecocatalysis. Ecocatalysts enriched in manganese, Eco-Mn, have demonstrated interesting and promising catalytic activities in several reactions.Regarding the good results achieved by ChimEco in ecology and in chemistry with accumulating plants and resulting Eco-Mn, it is necessary to better and precisely characterise Eco-Mn catalysts, by considering them as innovative materials, in order to understand and foresee their catalytic activity. This PhD work belongs within this context.Several analyses have been performed to characterise Eco-Mn catalysts. First, ICP-MS enables to identify metallic composition of Eco-Mn. Besides, XRD analyses highlight the presence of complex crystallized manganese salts, like K3NaMnCl6. Finally, X-ray absorption spectroscopy enables us to study the nature of manganese species which compose Eco-Mn catalysts, and to understand the oxidation states of Mn and Fe. Moreover, acid properties of Eco-Mn were demonstrated thanks to the study of a cyclic acetal rearrangement and infra-red spectroscopy of adsorbed pyridine. All these analyses were performed in order to determine first the composition of Eco-Mn catalysts, and secondly to highlight their physico-chemical properties, their oxidation state and their acid properties. Furthermore, this study also enable us to better understand the different steps of the ecocatalysts production process. Finally, synthetic catalysts were also produced and analysed in the same conditions as Eco-Mn, in order to bring out the specificities of Eco-Mn
Befort, Nicolas. "Pour une mésoéconomie de l'émergence de la bioéconomie : représentations, patrimoines productifs collectifs et stratégies d'acteurs dans la régulation d'une chimie doublement verte." Thesis, Reims, 2016. http://www.theses.fr/2016REIME001/document.
Повний текст джерелаThis thesis analyses the emergence of a new economic space from a mesoeconomic regulationist and evolutionist approach. This space has been called "bioeconomy" by the actors after divergent and conflictual interpretations of this concept. This economic space differs from the traditional ways of representing the division of labour into sectors (chemistry, agriculture, energy). The actors involved in seeking to define this space are reconstructing these sectors into an original and specific field, which is built on the use of biobased plant, animal and algal renewable resources. These actors consider themselves to be becoming the "industry of industries". Thus, instead of providing end products, they produce intermediates for agro- or chemical industries, materials or energy. The field does not cover photovoltaic electricity. Therefore, bioeconomy is a recomposition of the relationships between agriculture and chemistry in which the former becomes the supplier for the latter. We use the concept of the regimes of production of knowledge and of economic activity to describe the diversity of the technological promises made by the actors involved. We show, therefore, that bioeconomy cannot be reduced to the biotechnological revolution. Three broad views of bioeconomy emerge. At a deeper level, we present here three case studies to illustrate this diversity. The actors are weighed down by an "economy of promises" based on their own productive heritages that they are trying to reproduce and project into the future. This leads them to problematize the bioeconomy space in order to determine their resource allocations
Demory, Emilien. "Des esters arylboroniques aux arylnitrones : synthèse d'esters arylboroniques et nouvelle réaction d'arylation de nitrones cycliques." Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00819878.
Повний текст джерелаSkrzypczak, Valentin. "Développement de nouveaux composés biosourcés par oxydation catalytique et fonctionnalisation de l’isosorbide." Thesis, Lille 1, 2019. http://www.theses.fr/2019LIL1R063.
Повний текст джерелаFor several years now, environmental issues are increasing in the common mind. Indeed, the decrease of fossil resources is forcing the players in the world of chemistry to move towards other resources to develop a green and sustainable chemistry. This includes the use of renewable resources. Research and development of new environmentally biomass-based molecules is an integral part of green chemistry.Currently, there are several platform synthons derived from biomass that can be used in this chemistry. Among these synthons, isosorbide is one of the most used biobased molecules. His physicochemical and structural properties are very interesting and allow it to be used in different fields of chemistry. However, Isosorbide has two alcohol functions that can limit his reactivity. Therefore, this project aims to modify these alcohol functions to create new functions with the use of an ecofriendly method.First of all, the goal is to oxidize the hydroxyl functions of isosorbide by organometallic catalysis. The reactivity of the two hydroxyl groups and the influence of the different parameters establish on this oxidation reaction were studied. Different carbonyl derivatives have been produced and have undergone several transformations in order to increase their polarity. The point is to obtain potentially amphiphilic molecules
Hammami, Nadia. "Synthèse et étude des propriétés physico-chimiques de polymères biosourcés à base d'isosorbide." Thesis, Montpellier, 2018. http://www.theses.fr/2018MONTS127.
Повний текст джерелаThis research work aims to valorise isosorbide (IS) for biobased polymeric materials using original methods. After a short introduction of this molecule, we presented the different synthesis pathways and application fields of chemical and polymers already developed in scientific community. These compounds are classically obtained through many functionalization/synthesis steps with processes far away from green chemistry. Our first strategy based on the development of polyacetals derived from isosorbide (PAIS) was explained. A reaction scheme involving isosorbide with methylene halogenate in a non-toxic solvent (DMSO) was retained. The influence of different experimental parameters (stirring mode, reaction period and stoichiometry) was carefully analysed. Best results were achieved with high-speed mechanical stirring (more homogenous reactive solution, quantitative yield). The highest isosorbide concentrations led to the exclusive production of linear polyacetals (L-PAIS) whereas a low concentration under magnetic stirring conditions induced the formation of cyclic oligomers. Other macro-cycles (C-PAIS) with high molar weight were also produced. These different kinds of PAIS were characterised by various techniques (NMR, MALDI-TOF FTIR, SEC). Their physicochemical performances were also studied (TGA, DSC, rheology…) The length increase of polymer L-PAIS chains being challenged by cyclisation, we also explored lactide use (L- and racemic) as chain extender first by the reaction with IS then with L-PAIS. The La organometallic catalysis was more efficient than enzymatic pathway (PS lipase). Both chemical and physical analyses carried out with four polymeric grades derived from IS et lactide showed the added value of isosorbide molecule. Precise and reliable "structure-properties" relations including durability study were also led. Finally, similar approach could be applied for producing linear copolymers (PLLA-b-PAIS-b-PLLA and PRLA-b-PAIS-b-PRLA)
Yabre, Moussa. "Méthodes d'analyses innovantes et peu polluantes pour le contrôle qualité des médicaments essentiels : application aux antipaludiques." Thesis, Bordeaux, 2020. http://www.theses.fr/2020BORD0246.
Повний текст джерелаThe quality control of pharmaceutical products is a key issue in the medicine supply chain. It guarantees the reliability before consumption and contribute to fight against substandard and falsified drugs. It is conventionally performed according to pharmacopeias in which methods are most often long and use harmful reagents for the technical staff, health, and environment.The objective of this work was to improve the quality control of drugs through the development green analytical methods easy to implement in laboratories including those with limited resources. It was consisted, particularly, to develop reversed phase-high performance liquid chromatography methods with mobile phases based on ethanol which is one the best green solvents. Analyzes were applied to the antimalarial combination therapies such as artesunate/amodiaquine and artemether/lumefantrine.The first part of the study started by a screening phase where impacts of critical parameters, such as mobile phase pH and stationary phase, on compound peak symmetry, retention and detection were investigated. Artesunate/amodiaquine combination therapy, which includes an acidic compound with few chromophores and a basic compound was chosen as proof of concept. Several pH modifiers selected for their ecofriendly character and stationary phases were screened. Based on the screening results, different green RP-HPLC methods using ethanol as organic solvent et allowing to analyze artesunate, amodiaquine and their related impurities were developed. Quality by Design approach, recommended by the pharmaceutical regulatory authorities and allowing to obtain robust methods, was chosen as development strategy. Developed methods were validated according ICH Q2 (R1) guideline by using accuracy profile methodology.The second part of the study consisted in investigating the qualitative performance of a low-cost handheld near infrared spectrophotometer associated to chemometric methods as screening tool in the identification of falsified drugs. Analysis was performed on artemether/lumefantrine tablets which are one of the most falsified drugs, Despite its limited spectral range and low resolution compared to bench top devices, the handheld device allowed to detect falsified drugs with no active ingredients and to identify specifically a tablet brand name. This innovated low-cost handheld near infrared spectrophotometer offers a promising performance and could be used as a first line screening tool in the detection and fight against falsified drugs. For a better interpretation of the near infrared results, a green and fast HPLC method was also developed, validated, and used to analyze artemether and lumefantrine in the tablets.These different approaches demonstrated that green analytical methods could be implemented in the pharmaceutical quality control field without the need of new equipment and with analytical performances in accordance with pharmaceutical requirements
Prosa, Nicolo. "Synthèse supportée d'hétérocycles en milieux éco-compatibles : étude des conditions par lots et en flux continu. Purification par ultrafiltration en phase aqueuse." Phd thesis, Université Paris Sud - Paris XI, 2011. http://tel.archives-ouvertes.fr/tel-00664999.
Повний текст джерелаGonnet, Lori. "Mécanosynthèses organiques : étude cinétique de la réaction de Diels-Alder et synthèses de 1,2,4-triazoles à activités biologiques." Thesis, Ecole nationale des Mines d'Albi-Carmaux, 2019. http://www.theses.fr/2019EMAC0011.
Повний текст джерелаThis thesis project aims at developing green processes by medicinal mechanochemistry. It contains two parts. First, the Diels-Alder reaction mechanism using mechano-chemistry in comparison with the reaction in solvent medium was studied. The impact of process parameters for a vibratory ball mill was assessed. Grinding material, size and mass of the balls were studied, as well as the temperature of the milling media, providing apparent activation energy (Ea). In addition, different pathways for the synthesis of 1,2,4-triazole derivatives using mechanochemistry were developed. The biological activities of these compounds against M. Tuberculosis were evaluated. This thesis aims to lay the foundations for future scaling-up of green mechanochemical processes, analyzing the mechanisms, in order to formulate rules of general scope. This thesis, supported by the Occitanie Region, is based on the synergy of complementary skills of RAPSODEE (Albi) and SPCMIB (Toulouse) laboratories
Ghadban, Ali. "Synthèse et caractérisation de glycopolymères à base d'oligoalginates en milieu aqueux." Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00923140.
Повний текст джерелаTan, Jia-Neng. "La chimie des carbohydrates en milieu aqueux et dans des solvants bio-sourcés : Utilisation du glycosyloxyméthyl furfural (GMF) et analogues dans la réaction de Baylis-Hillman." Thesis, Lyon, INSA, 2015. http://www.theses.fr/2015ISAL0015/document.
Повний текст джерелаThis thesis is an exploration of the use of biosourced furanic aldehydes, namely hydroxymethyl furfural (HMF) and analogues, as a substrate for the Morita-Baylis-Hillman (MBH) reaction. The scope of the reaction has been explored, with a focus on the possibility to perform the reaction in aqueous or biobased medium. First, the MBH reaction of the glucosyloxymethylfurfural (GMF) with acrylic building blocks has been explored, led to two new series of glycoderivatives containing α-hydroxyacrylates and α-methylene-β-amino acrylates in fair yields. For the coupling reaction which produces the α-hydroxyacrylates, water can be used as the solvent. Mixtures of water and dimethylisosorbide (DMI) have also been shown to be possibly used in the reactions, allowing replacement of dioxane or THF compared to previous methods. The strategy is atom-economical. Due to the fact that those acrylic esters are also available from biomass, such kind of glycoacrylates appears as possibly 100% bio-based. The aza-MBH version of the reaction was further explored, studying the reaction involving the three components GMF, sulfonamides and a Micheal acceptor, leading to carbohydrate-based α-methylene-β-amino carbonyl derivatives. The focus was then made on HMF itself. Several biobased solvents, in particular 2-hydroxymethyl THF and isopropylideneglycerol, could be used for the MBH reaction of HMF and ethyl acrylate. For HMF and furfural, the reaction was improved when water was added allowing to widen the range of biobased solvent systems. We have also found that the bicyclic imidazolyl alcohol DPI is an efficient catalyst for the aqueous MBH reaction between HMF, furfural, GMF, and cyclic enones that gives access to a variety of potentially very useful molecules in an efficient and environmentally friendly way
Renault, Emmanuel. "Délignification du bois de châtaignier par une approche de chimie verte : Mise en œuvre et impacts sur la structure et le potentiel anti-radicalaire des phyto-polysaccharides extraits." Thesis, Limoges, 2014. http://www.theses.fr/2014LIMO0076/document.
Повний текст джерелаFractionation of wood, essential for the development of its molecular constituents, generally includes non eco-friendly steps. The key-step of the fractionation, the delignification, is generally based on the implementation of aggressive conditions, using harmful reagents, particularly chlorinated. In this work, we developed a new method of delignification of sawdust chestnut, emblematic species of the Limousin region, using phthalocyanine or porphyrin as a catalyst and hydrogen peroxide as the oxidant. Lignin degradation was characterized by various techniques, including FT-IR spectroscopy, UV-visible absorption and by measuring the kappa number. Then we showed that the use of phthalocyanine, less effective that porphyrins in terms of degradation mass yields of lignocellulosic material are however more selective to lignin oxydation. It was then possible, from residues only partially delignified, to extract by a simple hot water a hemicellulose with a similar structure to the 4-O-M¨¦thylglucuronoxylans classically extracted from hardwood. This polysaccharide is characterized by the presence of phenolic residues providing it an interesting antioxidant activity, measured against the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) by Electron Paramagnetic Resonance (EPR) and its IC50 is estimated at 225¦Ìg. mL-1. This value, compared to reference products such as vitamin E, allows to classify this compound among good candidates for development as a natural preservative for food or cosmetic industries
Konnert, Laure. "Préparation par mécanochimie de dérivés d'acides aminés et d'hydantoïnes." Thesis, Montpellier, 2015. http://www.theses.fr/2015MONTS279.
Повний текст джерелаThe development of environmentally-friendly chemistry has to go through the search for solutions concerning the use of organic solvents. Such solvents are often toxic and volatile, and create, especially in the case of halogenated solvents, environmental damage. The primary objective of this project is to develop alternatives to the use in synthetic chemistry of toxic and volatile organic solvents. Specifically, the goal is to develop methods of chemical transformations that can greatly reduce the use of solvent or replace them with alternative solvents. The development of these methods by mechanochemistry enabled to achieve this goal. Several methodologies have been developed and applied to the protection of amino acids and the synthesis of bioactive molecules such as hydantoins, including the preparation of pharmaceutical compounds such as phenytoin and ethotoin, two drugs prescribed against epilepsy
Ibrahim, Farah. "Synthèse de nouveaux matériaux de type calix-salens et applications en catalyse asymétrique hétérogène." Thesis, Paris 11, 2013. http://www.theses.fr/2013PA112002/document.
Повний текст джерелаChiral salen complexes have been intensively studied because they constitute one of the main catalyst families that can be used to prepare valuable, highly enantioenriched synthons. In line with the idea of green chemistry, one major goal is now to establish efficient procedures for the recovery and reuse of such catalysts. Several heterogenization procedures have been described that involve the modification of the salen structures through covalent grafting or non-covalent interactions with various supports. Another approach consists in the preparation of polymers from appropriately modified salen or corresponding complexes. In this context, the most common procedure involves polycondensation reactions between properly modified diamines and disalicylaldehyde derivatives.We have thus developed a polymer synthetic methodology by polycondensation of various modified disalicylaldehyde derivatives with different chiral diamines. Maldi-Tof analyses showed that the targeted polymers possessed a macrocyclic structure, named calix-salen, in a mixture of 2-, 3-, 4- and 5-mers. These new chiral calixsalen derivatives have been complexed with chromium and cobalt salts and tested as heterogeneous catalysts in asymmetric reactions (Henry Reaction, Hydrolytic Kinetic Resolution). After reduction of the imine functions, the corresponding reduced catalysts will be complexed with copper salts and tested to promote the Henry reaction for a comparison of the efficiency of both catalysts type. Their recyclability was examine
Rubulotta, Giuliana. "Catalytic Conversion of Biogenic Substrate into Valuable Building Blocks." Thesis, Lyon, 2016. http://www.theses.fr/2016LYSE1250.
Повний текст джерелаThe goal of this PhD project was in an early stage to study the activities of several commercial metal nanoparticles based catalysts for the mild hydrogenation of limonene. The hydrogenation of limonene has been performed in neat limonene and under mild conditions, e.g. low temperature (30°C) and low molecular hydrogen pressure (3 bar), aiming at a sustainable production route for (+)-p-1-menthene. In our study, the active metal nanoparticles (Pt, Pd and Ru) and supports (carbon, silica and alumina) were systematically varied and tested. It was found that the heterogeneous catalyst Pt/C alongside Pt/Al2O3 under mild reaction conditions (room temperature and 3 bar H2) was highly active and selective in the reduction of R-(+)-limonene to the partial hydrogenation product (+)-p-1-menthene. Moreover, the catalytic activity and stability of Pt/C were maintained during recycling tests under batch conditions and thus allowed the implementation of this catalytic system into continuous flow operation. The selective hydrogenation of terminal C=C bond over the internal one in limonene was rationalized by detailed kinetic studies which revealed an 8-fold difference in reaction rate between the two reactions. This previous study with commercial catalysts gave the possibility to tune the synthesis of heterogeneous metal-based catalysts for the next step of the study, where different heterogeneous metal based catalysts (Pt, Ru, Pt3Sn, and Ni), developed from a colloidal-based approach were tested in the hydrogenation of limonene. Those catalysts contain the same metal loading and similar particle sizes (ca. 2 nm) homogeneously dispersed onto non structured oxides (silica and alumina), carbon, or embedded into the walls or at the pore surface of a mesostructured silica materials (SBA-15). All the catalysts from the Pt series were particularly active in the selective hydrogenation of limonene towards p-menthene with further conversion into p-menthane, showing a very high reaction rate. Among of all those catalysts, the one containing Pt nanoparticles embedded in the walls of the silica showed the highest TOF, of ca. 2200 h-1 after two hours of reaction and a maximum yield in p-menthene of ca. 85 % was obtained after 10 hours of reaction. The same catalyst was tested in a continuous flow system and a stable yield of ca. 80% during 6 hours of reaction was reached. No products of isomerization were detected in the crude mixture during the reaction. We could therefore conclude that, using either a heterogeneous commercial catalyst like Pt/C or using a heterogeneous metal based catalyst developed from a colloidal-based approach like SBA-15{walls}, it was possible to achieve a selective conversion of limonene into p-menthene in batch and in continuous flow conditions