ANR 2015 - CO3SENS - CObalt Corroles for CO SENSors

The possibility of building wireless measurement systems has opened a very intense activity in the field of environmental control and risks. Our daily environment consists of many toxic components, including carbon monoxide (CO), which can be the cause of fatal poisoning. A real need exists to develop sensors that can easily detect and accurately track small concentrations of CO in the air. Another key application of CO sensors is the development of online monitoring and diagnostics systems for reliable and durable fuel cell system operations, since their efficiency is very sensitive to even small traces of CO. The consortium presented in this research project proposes to build a complete CO detection system based on a known precision microbalance quality associated with a specific organic functionalization (e.g. cobalt corroles). Strong complementarities between teams in terms of research and development (associated with high-level academic laboratories) and the possibility to transfer the complete technology for volume production (associated with one industrial) is an essential asset of this project. The current CO sensors are limited either by a low selectivity towards other gases or by a low sensibility, and no rational methodology or integrated approach to fine tune a sensing device for the particular application of CO detection has been developed so far. Our approach is clearly different from the known CO sensor technologies since we propose the use of molecular complexes or functionalized porous materials with specific reactivity towards CO to enhance the sensitivity and selectivity of the sensing layer. The objective of CO3SENS is to address this challenge.

ANR 2015 - JCJC "PORFUSION" - Electrochemically-driven Pi-extension of porphyrins

Pi-extension of porphyrins, i.e. fusion of one or several aromatic hydrocarbon(s) or aromatic heterocycle(s) onto the porphyrin periphery by intramolecular chemical oxidative coupling has attracted much attention because of potential applications in Near-IR electroluminescence displays, photovoltaic solar cells, non-linear optical materials, photodynamic therapy and molecular electronics. However, as mentioned in 2013 by Osuka, “New efficient fusion reactions under milder conditions are highly desirable in future developments”. For this purpose, as reported in 2012 by Gryko, “a better understanding of the mechanism of these intramolecular oxidative couplings is needed, specifically which moiety (porphyrin or the second aromatic system) is first attacked by the oxidant”. 
Thus this project will take advantage of electrochemistry and theoretical calculations to investigate fusion reaction mechanism with unprecedented peripheral aromatic fragments. Besides, this fusion reaction will be performed by electrosynthesis under mild conditions.

Principal Investigator: Dr Charles Devillers

ANR 2015 - OUTSMART - Organic materials for sensing applications

OUTSMART aims at exploring an efficient new methodology for synthesizing luminescent ionic materials for sensing applications in several domains. The main targets include radiation detection, small molecules sensing and the development of prototype sensors to break current technological limitations and address risks and threats of technological accidents, malicious terrorism but also for monitoring analysis of radiations and industrial facilities.

ANR 2016 - ALCATRAS - Adaptive hybrid ligands for Catalysis: new routes for activating stable C–H and C–O bonds

The present program is a fundamental research project aimed at developing innovative catalytic tools for specifically addressing at short- and mid-term, respectively, two contemporary synthetic industrial challenges: i) the regioselectivity limitations of metal-catalysed direct C–H functionalization of heteroaromatics, and ii) the restrictions in organocatalytic (non-metal) C–O bond activation within CO2 resource. We propose, on the basis of air-stable, temperature-robust versatile ferrocenyl platform (Fc), to design new hybrid acidic (Brønsted and Lewis acids) phosphine ligands with adaptive structures. Additionally, the ferrocene ligand synthesis proposed herein, because of this adaptive aspect, allows also for the synthesis of novel methylamino/borane species that can be valued in further organocatalytic (non-metal) catalysed C–H functionalization of heteroaromatics. Thus, entire new classes of ligands would be designed from a careful structure/reactivity approach (experimental and computational), and would provide auxiliaries for palladium-catalysed C–H functionalization with new selectivity, as well as potentially marketable organocatalysts for CO2 activation and heteroaromatic C–H functionalization – beyond the current proofs of concept. Owing to the robustness and versatility of the targeted tools the potential for industrial application would be much reinforced. 

This project, in addition to address several fundamental aspects (cooperative ligands in metal and organocatalysis) adequately suits the terms of the call Axe 4: “Chimie Durable, produits, procédés associés” in the “Défi 3 : Stimuler le renouveau industriel”. Several claims in the call perfectly fit the present project, i. e.: “La chimie doit aujourd’hui répondre aux enjeux du développement durable …Pour cela, elle doit accélérer l’évolution de ses pratiques pour réduire sa consommation en matières premières, son coût énergétique et son impact environnemental…la recherche de matières premières alternatives activation du CO2, de molécules C1-C3…”. The applied objective fits the terms of the call concerning “La catalyse est un principe essentiel de la chimie durable et au cœur des grands défis industriels de demain. Les innovations attendues concernent : (i) tous les types de catalyse à savoir … catalyse organométallique, organocatalyse…”. As mentioned above and further detailed below concerning “Adaptive hybrid ligands”, the bifunctional ferrocenes we propose for development (phosphino/carboxylate, phosphino/borane, amino/borane) are the results of a rational conception based on the robustness of the ferrocene platform, intramolecular CMD concept, and Lewis pairs chemistry. Thus, as mentioned in the call this was done for generating innovation “Afin de favoriser l’émergence de ces innovations, une approche basée sur la conception rationnelle (relations structure…) des catalyseurs est à privilégier.” Since the Dijon-Rennes consortium in previous projects successfully designed ligands for promoting difficult C–H functionalization: ligands which are now commercialized and available worldwide, the credibility of this consortium is recognizable. Its extension to international cooperation with a north-american research group of the highest level is also a strong point of this ANR project.

ANR 2016 - AZAPCO2 - Azaphosphatranes in confined space for CO2 valorization

The AZAP-CO2 project brings together researchers from supramolecular chemistry, materials science and theoretical chemistry to produce metal-free highly engineered molecular, supramolecular and nested catalytic cavities to catalyze the enantioselective cycloaddition of carbon dioxide to substituted epoxides. The use of carbon dioxide, a renewable feedstock, to produce cyclic carbonates is particularly attractive both for carbon management and sustainable development.

ANR 2016 - CARGOLD - Superparamagnetic nanoflowers

Superparamagnetic nanoflowers: bioresorbable carriers of ultrasmall gold nanoparticles designed for early detection of atherosclerosis by integrated MRI/PET imaging

Atherosclerosis is a chronic systemic inflammatory disease affecting the large and medium-sized arteries. The development of atherosclerosis which can progress silently during decades is characterized by the thickening and loss of elasticity of the arteries owing to the formation of atherosclerotic plaques in lesion-prone areas. These plaques are built from the accumulation of fatty materials within the vessel walls and by the modification of the connective tissue of the vessel walls. As a result, the luminal narrowing (stenosis) of the modified arteries occurs and limits therefore the blood flow which can lead to tissue ischaemia. However the most severe complications arise from the rupture of the atherosclerotic plaques which accounts for 70% of heart attacks. Since atherosclerosis is involved in most cardiovascular diseases which are the leading cause of morbidity and death in the world, the identification of vulnerable plaque (i.e. rupture-prone plaques) constitute an urgent need which would result in health benefits. Among the numerous imaging modalities, the combination of magnetic resonance imaging (MRI) and positron emission tomography (PET) constitutes a promising strategy because it allies the high resolution of MRI to the exceptional sensitivity of PET imaging. Such a combination should be a significant breakthrough in the early detection of vulnerable atherosclerotic plaques. If the development of imaging device which integrates both MRI and PET is in itself a major challenge, the elaboration of nanoprobes for exploiting this promising hybrid technology for medical imaging represents a crucial step for the early detection of vulnerable atherosclerotic plaques. Facing the real and urgent need, the CARGOLD project aims at developing nanoprobes for early detection of vulnerable atherosclerotic plaques and therapy by magnetic hyperthermia from multifunctional nanostructures whose physical and chemical properties render possible the specific targeting of these plaques, their follow-up by integrated MRI/PET device and also by computed tomography (CT) after intravenous injection, a therapeutic activity and their removal by bio-degradation and renal clearance. Such attractive characteristics should be obtained by assembling in a controlled manner bio-resorbable maghemite nanoflowers and multifunctional gold nanoparticles. The gold cores which can generate the contrast enhancement of the images acquired by CT will be coated by bio-targeting groups (peptides) and by gadolinium and positron emitter chelates for a simultaneous follow-up by MRI and PET. Although these multifunctional gold nanoparticles exhibit the potential for a targeted imaging, they are handicapped by a too rapid renal clearance which should impede a sufficient accumulation in the vulnerable plaques. Their grafting onto bio-resorbable nanocarriers (iron oxide nanoflowers (~30 nm)) is expected to enhance their circulation time after intravenous injection by postponing their renal clearance which remains a pre-requisite for the in vivo application of gold nanoparticles. Besides a greater circulation time, the accumulation of these golden nanoflowers designed for multimodal imaging (MRI/PET and CT) will be ensured by the avidity of macrophages for nanoparticles which are present in a large amount in the vulnerable plaques and by the specific interaction between the peptides coated to the golden nanoflowers and cell adhesion molecules (VCAM-1). This strategy carries the promise to significantly improve the detection of vulnerable plaques and therefore to prevent from the dramatic issue of their rupture. For achieving this ambitious goal, the CARGOLD project gathers six partners (4 academic partners, 1 medical imaging platform and an industrial specialized in the production of customized particles) which are recognized for their expertise in the complementary fields explored in CARGOLD.

ANR 2016 - HYBRIDIAMS - Hybrid Diamond-Metal Structures from Diamondoids: Synthesis and Catalytic Applications

The HYBRIDIAMS “Hybrid Diamond-Metal Structures from Diamondoids: Synthesis and Catalytic“ project aims at exploring the reactivity and exploiting the properties of molecular organic, thermodynamically extremely stable and highly regular, nm-sized carbon cages named diamondoids This project based on a combined experimental and theoretical approach aims at designing novel hybrid structures for which unobserved physical and catalytic properties are expected. This project concerns the development of the potential of diamondoids as building blocks for nanoscience and catalysis using approaches with several already obtained innovative proofs-of-concepts. 

ANR 2016 - ICARE_1 - Innovative Carbon@Metal Nanostructures for Sustainable Catalysis

Catalysis is the essential technology for precisely transforming the chemical structure of matter on a large scale. It lies at the heart of our quality of life, and it is also essential to a healthy economy. One of the main challenges for catalysis in the 21st century is to better understand and thereof design new catalyst structures in order to control more efficiently the catalytic activity, selectivity and stability. It is thus necessary for France to move forward and to develop innovative catalysts in order to “stimulate industrial revival”. Designing catalytic nano-architectures offers the promise of higher activity, selectivity and stability, provided the following specifications are followed: i) a precise control of nanoparticle (NP) size or shape, ii) a control of the direct environment of the NP, and iii) a robust and controlled (covalent) metal-support interaction. This is far from being the case on conventional supported catalysts, since particle size distribution are often quite broad, and due to the complex support surface chemistry, the nature of the metal support interaction is not precisely controlled, resulting in non-optimized catalytic performances. The ICARE_1 project focuses on the design of totally innovative heterogeneous catalysts. Inspired by Metal-Organic Frameworks we propose to develop a totally original family of hybrid materials, named metal-carbon frameworks (MECAFs), associating in a controlled manner and through covalent bonds, sp2–C and sp3–C nanostructured carbon materials with metallic NPs. The nanostructured carbon materials selected include C60 fullerenes and molecular nanodiamonds (NDs) derived from adamantane and diamantane. The controlled functionalization of nanocarbons in combination with the covalent bonding should ensure directionality in the assembly; chains (1D), planar (2D) or 3D assemblies are targeted. Additionally, the kinetic/thermodynamic control of the reaction should allow the construction of metallic NPs atom per atom, which is up to now impossible. This material should thus combine: i) a controlled NP size (an atom per atom NP construction is aimed), ii) an atomically-defined environment for the NPs, iii) a covalent interaction with the support, and iv) a high porosity and a highly dense surface area availability of the catalytic centers. To reach this objective an interdisciplinary approach is necessary; we thus strongly rely on consortium expertise for: i) the synthesis and functionalization of C60 and NDs, ii) the synthesis and characterization of metallic NPs for which metals such as Au, Ru and Pd are targeted because of their valuable catalytic applications, iii) the controlled assembly of hybrid structures, and iv) a computational approach aimed at modeling and understanding the formation of such mixed edifices construction. We will apply MECAFs to a strategic domain of catalysis in industrialized countries: fine chemical synthesis. Two reactions of high industrial interest have been selected, for which catalytic activity, selectivity and stability are genuine challenges: i) the hydroaminomethylation reaction that allows producing amines from alkenes, and ii) the direct arylation of unactivated C–H bonds in heteroaromatics that sustainably bring diversity in fine chemicals synthesis. We will specifically search information linking structure and reactivity/selectivity. Such a groundbreaking material assembly would be very innovative, and the potential for scientific and technological progresses is enormous. Besides catalysis, MECAFS should be of great interest for chemists and physicists. For example the study of the magnetic and transport properties of magnetic MECAF should be very exciting for physicists. For chemists, the chemical reactivity of atomically defined NPs is an exciting perspective. Additionally, the possibility to reach high metal loading and high dispersion offer interesting perspective for electrocatalysis or for gas storage.

ANR 2016 - JCJC "SPID" - Smart Probes for Imaging metal-based Drugs

Metal complexes are widely used for the treatment of numerous pathologies (cancer, rheumatoid arthritis, osteoporosis…). Despite their use in clinics, their mechanisms of action are still poorly known. An elegant way to elucidate them is to synthesize labelled therapeutic agents that can be tracked in vitro and in vivo by medical imaging. The problem of most reported labelled drugs is the reliability of the information that they provide. Indeed, if the link between the probe and the therapeutic moiety is broken, the observed signal will only enable to track the label moiety. So knowing if this link is broken or not is crucial.
The main aim of this project is to design “smart probes” that can enable the tracking of metal based drugs and at the same time give information on the state/integrity of the compound. Two types of probes will be investigated: “ON/OFF” probes which emit fluorescence (“on” mode) when they are attached to the metal centre and not when the metal decoordinates (“off” mode) and “multicolour” probes which display different fluorescent emission depending on the state of the complex.

Principal Investigator: Dr Ewen Bodio

ANR 2016 - MuSiC - Multiscale Simulations of Bifunctional Catalysts

In sustainable chemistry, the switch towards biomass-based resources requires to develop new catalysts for new reactions. Although simulation could be an excellent tool for the design of novel catalysts, the large size of the reaction network and the solvated conditions render brute force first principle calculations hopeless. In this project, we propose a novel multi-level and multi-scale approach to solve this issue and explore the complex pathways of the catalytic transformation of sugar molecules extracted from biomass using bifunctional catalysts. The complete reaction pathway, with hundreds of reactions, will first be mapped with a simple, approximate but very fast force-field approach. Kinetic simulation on that reaction array will dictate the few important elementary steps that need to be accurately calculated. This high level will be performed with state of the art hybrid multi-scale free energy barrier simulations, including full treatment of the solvent.

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