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PhD subjects

9 sujets INAC

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• Chemistry

Activation of carbon dioxyde by electron-rich metal complexes

SL-DSM-14-0161

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire de Reconnaissance Ionique et Chimie de Coordination (RICC)

Grenoble

Contact person :

Marinella MAZZANTI

CEA
DSM/INAC/SCIB/RICC

Starting date : 01-10-2014

Contact person :

Marinella MAZZANTI

CEA - DSM/INAC/SCIB/RICC

0438783955

Thesis supervisor :

Marinella MAZZANTI

CEA - DSM/INAC/SCIB/RICC

0438783955

More : http://inac.cea.fr/Pisp/51/marinella.mazzanti.html

The transformation of carbon dioxide is an important goal in contemporary catalysis. Indeed, this low cost and abundant molecule may provide an ideal renewable chemical feedstock for the production of fine chemicals and clean fuels. Natural photosynthesis by chlorophyll molecules involves the generation of carbohydrates from CO2. However, the chemical activation of carbon dioxide, meaning its cleavage in a chemical reaction is one of the biggest challenges in synthetic chemistry due to the high thermodynamic stability of the C=O bond. A possible way to overcome this intrinsic low reactivity is to design highly reactive metal complexes capable of binding CO2 and transferring a high number of electrons (2-6) to afford CO, CH3OH, or CH4. One of the highest challenges in the development of efficient catalysts for CO2/N2 reductions is to design complexes capable of multielectron redox reactions. This can be achieved by associating electron-rich metals to redox active ligands or by designing polymetallic complexes with strong donor ligands. The first strategy recently led our group to the preparation of lanthanide complexes capable of transferring up to six electrons to a substrate. Adopting the second strategy we have prepared polymetallic siloxide complexes of f elements which can selectively reduce carbon dioxide to afford CO and carbonate or oxalate. The goal of this thesis is to develop highly reactive complexes of d- and f- block transition metals associated to Lewis acidic metal ions and capable of multiple electron transfer. The properties of these complexes will be implemented by tuning the coordination environment with the objective of promoting the stoechiometric reduction of carbon dioxide. Then efforts will be directed to include these complexes in electro- catalytic cycles. The project will involve, organometallic synthesis, spectroscopy (NMR, UV, IR, ES/MS, EPR), X-ray diffraction, electrochemistry. The catalytic properties of the complexes prepared during the thesis will be tested by electrochemistry and gas-chromatography. The subject of this thesis is inscribed in the context of the fundamental research on renewable energy developed at the CEA.
Atomic Structure determination by Dynamic Nuclear Polarization enhanced NMR and ab initio DFT Calculations

SL-DSM-14-0410

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire de Résonance Magnétique (RM)

Grenoble

Contact person :

GAEL DE PAEPE

CEA
DSM/INAC/SCIB/RM

Starting date : 01-10-2013

Contact person :

GAEL DE PAEPE

CEA - DSM/INAC/SCIB/RM

04 38 78 65 70

Thesis supervisor :

Jean-Marie MOUESCA

CEA - DSM/INAC/SCIB/RM

04 38 78 30 13

More : http://inac.cea.fr/Pisp/gael.depaepe/

Context: Advanced DNP enhanced Solid-State NMR Methods and DFT Calculation for the studies of functionalized Silicon Nanoparticles / Self-assembled peptides / Structure of complex macromolecules



The SCIB at INAC (Institute for Nanosciences and Cryogenics, CEA Grenoble) has a PhD opening for a physical-chemist. This PhD deals with the development of an advanced atomic-level characterisation technique, namely solid-state DNP (Dynamic Nuclear Polarization) enhanced NMR (Nuclear Magnetic Resonance) combined with ab initio DFT (Density Functional Theory) calculations.

Many challenging systems (porous materials, self-assembled nano-assemblies, silicon nanoparticles/nanowires, etc.) are still lacking efficient atomic scale characterization techniques. This clearly impedes a deep understanding of their structure and thus any rational design yielding improved materials with optimized properties.

This PhD aims to push the limits of sensitivity and overcome such a limitation by demonstrating how DNP-enhanced solid-state Nuclear Magnetic Resonance (NMR) allows gaining new insights into the structure and dynamics of some of these challenging systems. The work will mainly consists in designing new methods (theoretical and experimental) to probe structure and dynamics of complex natural or nano-engineered systems at the atomic scale.

The SCIB laboratory in collaboration with the Bruker company (world leader in NMR instrumentation) is also pioneering the development of high field DNP and is currently operating the first High Field DNP experiment in France (since September 2011). The lab is also strongly involved in new instrumentation development: (i) an experimental setup, unique in the world, (Coll. with SBT, another laboratory of INAC) in order to achieve Helium spinning down to 10 Kelvin allowing access to very low temperature DNP measurements (ii) several original methods to enhance spectral resolution and extract structurally relevant constraints in solid-state NMR.

This project is interdisciplinary, since it involves sample preparation, developing innovative Nuclear Magnetic Resonance experiments, and advanced data interpretation through spin dynamics simulations and DFT calculations. This work will take place in a highly dynamical environment at the MINATEC campus (CEA Grenoble) involving the direct mentoring from one solid-state DNP specialist (G. De Paëpe) and one DFT specialist (J.-M. Mouesca).
Development of modifed graphene composites for electrochemical storage applications

SL-DSM-14-0185

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire de Reconnaissance Ionique et Chimie de Coordination (RICC)

Grenoble

Contact person :

Florence DUCLAIROIR

CEA
DSM/INAC/SCIB/RICC

Starting date : 01-10-2014

Contact person :

Florence DUCLAIROIR

CEA - DSM/INAC/SCIB/RICC

04 38 78 53 68

Thesis supervisor :

Lionel DUBOIS

CEA - DSM/INAC/SCIB/RICC

04 38 78 92 57

The expectations around graphene come from huge potentialities for various applications (RF transistor, (bio)sensors?). Graphene high specific surface, mechanical resistance and conductivity make it specifically attractive for electrochemical storage applications. Its interfacing with molecules has been shown to tune its electrical/optical properties and to create functional materials. Graphene has also been modified with mineral composites to target higher energy density. Conjugated polymers alone or associated with graphene7 for supercapacitors applications have been reported.

Based on this context, the goal of the project is to develop a graphene matrix functionalized with redox compounds (nitroxide, oligothiophene?) ? remaining in the monomer to oligomer range - that could be exploited for electrochemical storage applications. The ambitions of this project are to gain more insight on the physical and electrical properties of graphene, to gain and widen experimental skills on the synthesis, modification and characterization of graphene and also to study the electrochemical behavior (power evolution, structural ageing) of the electrodes made from these materials.

Nano-sized luminescent devices based on lanthanide complexes

SL-DSM-14-0355

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire de Reconnaissance Ionique et Chimie de Coordination (RICC)

Grenoble

Contact person :

Marinella MAZZANTI

CEA
DSM/INAC/SCIB/RICC

Starting date : 01-10-2014

Contact person :

Marinella MAZZANTI

CEA - DSM/INAC/SCIB/RICC

0438783955

Thesis supervisor :

Daniel IMBERT

CEA - DSM/INAC/SCIB/RICC

+33(0)438783887

The lanthanide-based visible and NIR luminescence emission attracts a considerable interest in the field of lighting, light emitting diodes, light converters, optical fibres for telecommunication, logic gates, barcoded materials, labels for biomedical analysis, chiral recognition or sensors. In theses fields, the creation complexes, edifices or devices based on lanthanide (III) is obtained with the association of metals and organic chromophores. Application of the supramolecular chemistry to coordination chemistry is relatively recent and of a great interest for supramolecular architectures but has lagged behind that of other systems due to the difficulty in the control of the coordination environment of the ions.

In this project the synthetic methods for the incorporation of different lanthanide ions in monometallic complexes, polymetallic assembly, multidimensional coordination polymers and multicolour platforms will be developed. The objective is to provide systems with high luminescent quantum yield and sensitization of the lanthanide ions with excitation a low energy (350-450 nm). Nano-sized materials will be developed from these assemblies. This project involves organic synthesis of new ligands and small organic molecules, the synthesis of nanoparticles and the study of their coordination chemistry lanthanide ions using different spectroscopic techniques
Nanosized lanthanide-based supramolecular architectures: understanding, control and application to luminescent materials

Contact person :

Marinella MAZZANTI

CEA - DSM/INAC/SCIB/RICC

0438783955

Thesis supervisor :

Daniel IMBERT

CEA - DSM/INAC/SCIB/RICC

+33(0)438783887

More : http://www-drfmc.cea.fr/Pisp/51/marinella.mazzanti.html

More : http://inac.cea.fr/

The assembly of sophisticated molecular architectures containing lanthanide ions and organic/inorganic cromophores allows the combination of a nanoscopic size with the magnetic or optical properties of the metals leading to interesting new materials. The lanthanide-based visible and NIR luminescence emission attracts a considerable interest in the field of light emitting diodes, light converters, optical fibres for telecommunication, logic gates, barcoded materials, labels for biomedical analysis, chiral recognition or sensors. In theses fields, the creation of polymetallic and multimodal architectures is crucial for the design and the engineering of elaborate lanthanide-based edifices and devices. Application of the supramolecular chemistry to coordination chemistry is relatively recent and of a great interest for supramolecular architectures but has lagged behind that of other systems due to the difficulty in the control of the coordination environment of the ions which display high and variable coordination numbers with little stereochemical preferences. In this project the synthetic methods for the incorporation of different lanthanide ions in large polymetallic assembly, in multidimensional coordination polymers and multicolour platforms will be developed.

The subject proposed involves the organic synthesis of new ligands and the study of their coordination chemistry with divalent and trivalent lanthanide ions using different techniques including by X-ray diffraction studies, NMR, and electrospray studies. The photophysical properties will be investigated in detail, in solution and in the solid states. The application of the developed architectures to the construction of new luminescent devices and materials will be carried in fields ranging from applications in materials to biological imaging. We have already significant collaborations on the local (technological departments of CEA?), regional, national or international scales in various fields such as for anti-forgery fluorescent labels, X-ray imaging, organic light-emitting diodes (OLEDs) for flat panel displays, luminescent tags for biological molecules, sensors and contrast agents for magnetic resonance imaging (MRI).

Nucleic Acids based-Architectures as Bio-Inspired Scaffolds for NanoTechnologies (Acronym: NatureTech)

SL-DSM-14-0311

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire Lésions des Acides Nucléiques (LAN)

Grenoble

Contact person :

Didier GASPARUTTO

CEA
DSM/INAC/SCIB/LAN

Starting date : 01-10-2014

Contact person :

Didier GASPARUTTO

CEA - DSM/INAC/SCIB/LAN

04 38 78 45 48

Thesis supervisor :

Didier GASPARUTTO

CEA - DSM/INAC/SCIB/LAN

04 38 78 45 48

Nature has demonstrated an extraordinary capacity to assemble complex nanostructures with multifunctional and high reliability skills. Among all these assemblies, Nucleic Acids are biopolymers which encode the complexity of all life forms on Earth by containing the genetic blueprint, are arguably the most powerful media known for the data storage and processing. Due to the intrinsic properties of DNA, the conception of DNA-based architectures appears recently as a very exciting and promising field of research because it opens to the perspective of new devices and materials with applications in medicine, energy, electronics and photonics.



In the present research project we will work at the development of functionalized DNA-based architectures and bio-inspired assemblies for biological and technological applications. Firstly, the synthesis of modified DNA fragments (containing modified nucleobases, stable DNA analogs, branched structures, fluorescent dyes,...) will allow the development of new multiplexed nanobiosensors (bioprobes) or multivalent nanodrugs (inhibitors) to target enzymatic activities. Secondly, by inserting selective organic molecules into complex DNA architectures, new bio-hybrid materials and devices will be built with original intrinsic properties and potential applications in several fields of nanosciences (mainly in nanoelectronics, nanophotonics and spintronics).



Altogether, the present research project constitutes a cross-disciplinary program with a strong trainer character for the applying candidate and important synergies between several collaborative laboratories.

Oxigen reduction : a biomimetic approach

SL-DSM-14-0307

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire de Reconnaissance Ionique et Chimie de Coordination (RICC)

Grenoble

Contact person :

Lionel DUBOIS

CEA
DSM/INAC/SCIB/RICC

Starting date : 01-10-2014

Contact person :

Lionel DUBOIS

CEA - DSM/INAC/SCIB/RICC

04 38 78 92 57

Thesis supervisor :

Jean-Marc LATOUR

CEA - DSV/IRTSV/CBM/PMB

04 38 78 44 07

The main biological reaction involved in energy conversion involve complex enzymatic systems the actyiive site of which comprise multimetallic assemblies. A striking example is cyctochrome c oxidase that associate four metal sites to reduce dioxygen to water in a four electron process. This reaction bears a strong interest since it intervenes at the fuel cell cathode where it is catalyzed by platinum the price and availability of which cause limitations. These metal active sites very often associate metals of different nature that contribute synergistically to the electron transfers through polarization of the involved interactions. The project aims at studying the efficiency of heteropolymetallic systems to reduce dioxygen into water. The nature and oxidation states of the metals, the nuclearity and the geometry of the assemblies, the number and nature of the coligands are among the parameters used to orient and optimize the catalysts activity. Anchoring of the catalysts on inert supports will be used as a means to stabilize them.
Synthesis and characterization of new organic materials for application in dye sensitized solar cells

Contact person :

Renaud DEMADRILLE

CEA - DSM/INAC/SPrAM/LEMOH

04 38 78 44 84

Thesis supervisor :

Peter REISS

CEA - DSM/INAC/SPrAM/LEMOH

0438789719

More : http://inac-i.cea.fr/Pisp/renaud.demadrille/

More : http://inac-i.cea.fr/Phocea/Vie_des_labos/Ast/ast_groupe.php?id_groupe=429

More : http://www.kaironkem.com/

Among the new photovoltaic technologies, Dye-Sensitized Solar Cells (DSSC) technology has initiated its industrial development. This technology shows several advantages compared to silicon-based solar cells such as better performances in many non-ideal light environments (example dim, diffuse and indoor light) and a much lower energy payback time, besides DSSCs can be semi-transparent and colourful.

In this thesis project we will develop new organic sensitizers showing absorption spectra extended in the visible part of the solar emission spectrum over 650nm and in the near infra red. New aromatic heterocycles with an electron deficient character will be developed and incorporated in chemical structures allowing the preparation of oragnic dyes strongly absorbing in those spectral domains. In order to develop more robust and efficient solar cells, the replacement of liquid electrolytes that are commonly employed in the favrication of DSSCs is highly desirable. To replace liquid electrolytes we will develop new p-type molecules and polymers showing good charge transport properties and a high thermal and photochemical stability. using the reserach facilities of Hybriden and the equipêments available in SPRAM the new molecules will be incorportared and tested in real devices and their photovoltaic performances will be evaluated.
Understanding of uranyl chelation by biomolecules : design of biomimetic chelating peptides for detoxification

SL-DSM-14-0382

Research field : Chemistry

Location :

Service de Chimie Inorganique et Biologique (SCIB)

Laboratoire de Reconnaissance Ionique et Chimie de Coordination (RICC)

Grenoble

Contact person :

Pascale DELANGLE

CEA
DSM/INAC/SCIB/RICC

Starting date : 01-10-2014

Contact person :

Pascale DELANGLE

CEA - DSM/INAC/SCIB/RICC

0438789822

Thesis supervisor :

Pascale DELANGLE

CEA - DSM/INAC/SCIB/RICC

0438789822

More : http://inac.cea.fr/Pisp/pascale.delangle/

Heavy metals, especially actinides, are toxic for humans. Understanding the molecular mechanisms responsible for their toxicity is an important field of research in toxicology.

This PhD thesis aims first at identifying coordination sites of an important actinide, namely uranyl, in two proteins, which exhibit very high affinities towards this metal ion to bring some new insights into molecular mechanisms involved in actinide?s toxicity. A second objective will be the design of biomimetic chelating peptides inspired from these coordination sites for in vivo detoxification after nuclear terrorist attacks or accident in nuclear plants.

This multidisciplinary project at the interface between chemistry and biology will involve various concepts and methods:

- Solid Phase Peptide synthesis,

- Chelation analysis with mass spectrometry and several spectroscopies such as UV-visible, circular dichroism, luminescence and NMR,

- Structural analysis by solution NMR,

- Protein purification and characterization (circular dichroism, UV-visible, electrophoresis,?)

- Stability constants measurements by luminescence, capillary electrophoresis or Surface Plasmon Resonance.

 

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