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課題：water-soluble complexes in molecular and polymer chemistry : towards green chemistry and sustainable development 詳細(xì)內(nèi)容見(jiàn)附件，有意向的可以準(zhǔn)備好英文簡(jiǎn)歷聯(lián)系導(dǎo)師。有關(guān)于導(dǎo)師和法國(guó)的問(wèn)題可以聯(lián)系我，不常上小木蟲(chóng)，可以發(fā)郵件至zephyrtangyue@gmail.com更新：附件下不了，直接貼原文了： French Polytech network form for PhD Research Grants from the China Scholarship Council This document describes one of the PhD subjects proposed by the French Polytech network. The network is composed of 15 engineering schools/universities. The document also provides information about the supervisor. Please contact the PhD supervisor by email for further information regarding your application. Supervisor information Family name MICHELET First name VERONIQUE Email veronique.michelet@univ-cotedazur.fr Web reference https://icn.univ-cotedazur.fr/ax ... esis-fine-chemistry Lab name INSTITUT de CHIMIE de NICE Lab web site https://icn.univ-cotedazur.fr Polytech name Cliquez ou appuyez ici pour entrer du texte. University name COTE D’AZUR UNIVERSITY Country France PhD information Title Water-soluble complexes in molecular and polymer chemistry : towards green chemistry and sustainable development Green chemistry / Biomaterials and polymer materials / Sustainable development engineering and lower cost manufacturing Required skills in science and engineering Chemistry Subject description： Water-soluble complexes in molecular and polymer chemistry : towards green chemistry and sustainable development In the field of chemistry and in close collaboration with the U.S. Agency for Environmental Protection ("U.S. EPA"  , Paul Anastas and John Warner introduced the concept of "green chemistry" and promoted catalysis among the 12 principles.1 One of the key principles of "Green Chemistry " is to limit the use of volatile organic solvents in industrial processes. Indeed, these solvents are often toxic, expensive and problems are inherent to their disposal and reprocessing. A major research effort has been devoted to developing new synthetic methods that are more environmentally friendly. Among the atypical solvents, water seems to be the best choice because of its abundance (important economic benefits) and non-toxicity (reducing releases of persistent organic pollutants). Finally, water can be very effective in organic synthesis because of its very specific intrinsic physico-chemical properties (decreasing viscosity of water with increasing temperature, high specific heat, high surface tension, high dielectric constant). Historically the beneficial effect of water in the pericyclic reactions was described in 1980 through the Diels-Alder reaction between cyclopentadiene and methyl vinyl ketone. In the area of pharmaceutical derivatives, the production of a high value compound generally results in the production of waste, several very costly purification steps that may reach 50% of the cost of the process.2 Catalysis represents one of the key developments of modern chemistry: it allows the use of reagents in limited quantities (ideally equimolar), the saving of energy by increasing process aqueous phase aqueuse organic phase aqueous phase organic phase products aqueous phase reagent in organic phase organique stirring catalyst reagent product 3 | Page efficiency and also facilitates separation by increasing the selectivities of several reactions. Although heterogeneous catalysis allows an easy recovery of the catalyst by simple filtration, the effectiveness and selectivity of the heterogeneous methods are often lower. Conversely, homogeneous catalysis, which is particularly effective and selective and allows the use of milder conditions, required an often more challenging separation of the catalyst. To overcome this drawback, the use of alternative more environmentally friendly solvents, such as water, was envisaged and the concept of homogeneous catalysis in biphasic medium and developed to combine advantages of homogeneous catalysis and the ease of separation of the catalyst.3 In this case, the reactants and products are soluble in the organic phase, while the catalyst is dissolved in water. During the reaction, the reaction mixture is vigorously stirred and / or heated to allow the catalyst/substrates interactions. At the end of the reaction, the catalyst is recovered and recycled by simple decantation. Due to their high coordinating properties, the main water-soluble ligands are based on phosphines bearing ionic or neutral polar hydrophilic groups; soluble sulfonated phosphine ligands being by far the most studied derivatives in the literature. We intend to develop during this PhD program novel methodologies to lead to elegant and original solutions in the synthesis of chiral building blocks for 2 applications: pharmaceuticals key intermediates and polymers. Part of the research program will be conducted in collaboration with international groups and will involve stay in European laboratories. The group of University University Côte d’Azur has gained international notoriety for catalysis in water4 and, for several years have developed catalytic reactions involving C-C bond formation in water or organo aqueous medium. 5 The research of the University Côte d’Azur has been recently devoted to the discovery and optimization of new systems. 6 One application will be devoted to the synthesis of key building blocks for industrial applications (pharmaceutical or fragrances). Another application will concern the use of the chiral building blocks for the preparation of novel polymers. The thermomechanical behavior and measurements of exchange rate reactions will be measured, taking into account the repairability, reprocessing and recycling of the materials. Another purpose will be to understand how different polymer chain networks could influence further material processing and properties. Bibliographie 1 Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998. 2 Eissen, M.; Metzger, J.O.; Schmidt, E.; Schneidewind, U. Angew. Chem. Int. Ed.2002, 41, 414. 4 | Page 3 a) Cornils, B. Org. Proc. Res. & Dev.1998, 2, 121. b) Aqueous Phase organometallic catalysis. Concepts and application, 2nd Ed., Eds: B. Cornils, W.A. Herrmann Wiley-VCH, 2004. 4 a) Le Boucher d’Herouville, F.; Millet, A.; Scalone, M.; Michelet, V. Synthesis 2016, 48, 3309. b) Leseurre, L.; Le Boucher d’Herouville, F.; Millet, A.; Genêt, J.-P.; Scalone, M.; Michelet, V. Catal. Commun.2015, 69, 129. c) Leseurre, L.; Püntener, K.; Genêt, J.-P.; Scalone, M.; Michelet, V. Adv. Synth. Catal.2011, 353, 3269. d) Le Boucher d’Herouville, F.; Millet, A.; Scalone, M.; Michelet, V. J. Org. Chem.2011, 76, 6925. 5 a) Genin, E.;Michelet, V. in Green Process Engineering – From Concepts to Industrial Applications Poux, M.; Cognet, P.; Gourdon, C. Eds, CRC Press Taylor & Francis Group, 2015: “Water as solvent and solvent-free reactions”. b) Leseurre, L.; Genêt, J.-P.; Michelet, V. in Handbook of Green Chemistry Series :Water as a Green Solvent P. Anastas, C.-J. Li Eds; John Wiley & Sons, 2010. 6 a) Michelet, V.; Scalone, M. Electronic Encyclopedia of Reagents for Organic Synthesis, Paquette L.; Fuchs, P.; Crich, D.; Wipf, P. Eds, John Wiley & Sons, 2015, 10.1002/047084289X.rn00832.pub2. b) Leseurre, L.; Le Boucher d’Herouville, F.; Püntener, K.; Scalone, M.; Genêt, J.-P.; Michelet, V. Org. Lett.2011, 13, 3250. c) Tang, Y.; Benaissa, I.; Huynh, M.; Vendier, L.; Lugan, N.; Bastin, S.; Belmont, P.; César, V.; Michelet, V. Angew. Chem. Int. Ed. 2019, 58, 7977. d) Laher, R.; Marin, C.; Michelet, V. Org. Lett. 2020, 22, 4058. e) Michelet, V. Chemical Record 2021, doi.org/10.1002/tcr.202100253. 7 Preliminary results: Mija, A.; Louisy, E.; Lachegur, S.; Khodyrieva, V.; Martinaux, P.; Olivero, S.; Michelet, V. Green Chem. 2021, DOI: 10.1039/D1GC02732H. |
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