Molecular Signature of Polyoxometalates in Electron Transport of Silicon-based Molecular Junctions

Polyoxometalates (POMs) are unconventional electro-active molecules with a great potential for applications in molecular memories, providing efficient processing steps onto electrodes are available. The synthesis of the organic-inorganic polyoxometalate hybrids [PM$_{11}$O$_{39}$(Sn(C$_6$H$_4$)C$\equiv$C(C$_6$H$_4$)N$_2$)]$^{3-}$ (M = Mo, W) endowed with a remote diazonium function is reported together with their covalent immobilization onto hydrogenated n-Si(100) substrates. Electron transport measurements through the resulting densely-packed monolayers contacted with a mercury drop as a top electrode confirms their homogeneity. Adjustment of the current-voltage curves with the Simmons equation gives a mean tunnel energy barrier of 1.8 eV and 1.6 eV, for the Silicon-Molecules-Metal (SMM) junctions based on the polyoxotungstates (M = W) and polyoxomolybdates (M = Mo), respectively. This follows the trend observed in the electrochemical properties of POMs in solution, the polyoxomolybdates being easier to reduce than the polyoxotungstates, in agreement with lowest unoccupied molecular orbitals (LUMOs) of lower energy. The molecular signature of the POMs is thus clearly identifiable in the solid-state electrical properties and the unmatched diversity of POM molecular and electronic structures should offer a great modularity

Transport and Phototransport in ITO Nanocrystals with Short to Long-Wave Infrared Absorption

Nanocrystals are often described as an interesting strategy for the design of low-cost optoelectronic devices especially in the infrared range. However the driving materials reaching infrared absorption are generally heavy metalcontaining (Pb and Hg) with a high toxicity. An alternative strategy to achieve infrared transition is the use of doped semiconductors presenting intraband or plasmonic transition in the short, mid and long-wave infrared. This strategy may offer more flexibility regarding the range of possible candidate materials. In particular, significant progresses have been achieved for the synthesis of doped oxides and for the control of their doping magnitude. Among them, tin doped indium oxide (ITO) is the one providing the broadest spectral tunability. Here we test the potential of such ITO nanoparticles for photoconduction in the infrared. We demonstrate that In2O3 nanoparticles presents an intraband absorption in the mid infrared range which is transformed into a plasmonic feature as doping is introduced. We have determined the cross section associated with the plasmonic transition to be in the 1-3x10-13 cm2 range. We have observed that the nanocrystals can be made conductive and photoconductive due to a ligand exchange using a short carboxylic acid, leading to a dark conduction with n-type character. We bring further evidence that the observed photoresponse in the infrared is the result of a bolometric effect

The one year fate of iron oxide coated gold nanoparticles in mice

Safe implementation of nanotechnology and nanomedicine requires an in-depth understanding of the life cycle of nanoparticles in the body. Here, we investigate the long-term fate of gold/iron oxide heterostructures after intravenous injection in mice. We show these heterostructures degrade in vivo and that the magnetic and optical properties change during the degradation process. These particles eventually eliminate from the body. The comparison of two different coating shells for heterostructures, amphiphilic polymer or polyethylene glycol, reveals the long lasting impact of initial surface properties on the nanocrystal degradability and on the kinetics of elimination of magnetic iron and gold from liver and spleen. Modulation of nanoparticles reactivity to the biological environment by the choice of materials and surface functionalization may provide new directions in the design of multifunctional nanomedicines with predictable fate

Nanoparticules bistables de réseaux de coordination à ponts cyanure

Les travaux de cette thèse s inscrivent dans le domaine de composés magnétiques bistables à l échelle nanométrique. Certains réseaux de coordination tridimensionnels à ponts cyanure de type analogues de bleu de Prusse, clathtrates d Hoffman et dérivés d octacyanométallates sont respectivement ferromagnétiques, à transition de spin et photomagnétiques. L aimantation de ces matériaux change, et ce de manière réversible, par application d un stimulus extérieur, notamment un champ magnétique, une irradiation lumineuse ou une variation de température. L objectif principal de cette thèse était de synthétiser des nanoparticules de ces réseaux et d étudier l effet d une telle réduction de taille sur leurs propriétés magnétiques. Ainsi, des nanoparticules de réseaux dérivés d octacyanométallates ont été synthétisées par stabilisation électrostatique dans l eau et l élaboration de systèmes cœur-coquille a permis un contrôle sur la taille et la composition des systèmes à l échelle nanométrique. Les propriétés photomagnétiques de certains nano-objets ont été caractérisées par différentes méthodes (SQUID, spectroscopie d absorption X) pour faciliter la compréhension du mécanisme de la photo-transformation et pour différentes mises en forme des nanoparticules (sous forme de poudre, en matrice polymère et organisées dans des films Langmuir-Blodgett) dans le but d améliorer la photo-transformation. Des nanoparticules d un réseau tridimensionnel de type clathrate d Hoffman Fe(pyrazine)M(CN)4 (M=Pt,Ni) ont été obtenues en microémulsion et le comportement de transition de spin d objets de différentes tailles a été étudié, indiquant une forte modification des propriétés par rapport au composé massif. Un autre aspect de ces travaux a consisté en l organisation de nanoparticules magnétiques sous forme de monocouche par greffage sur substrat de silicium fonctionnalisé par une monocouche organique mixte d accrochage. La caractérisation de nanoparticules superparamagnétiques de l analogue de bleu de Prusse CsNiCr(CN)6 greffées montre qu elles sont solidement accrochées sur la surface et conservent leur intégrité chimique et magnétique lors du greffage.This work is devoted to the synthesis and the study of bistable nanoparticles. The Prussian blue-like, Hoffman-like and octacyanometallate-based cyanide bridged three dimensional networks are able to switch their magnetic ground state as a function of an external perturbation such as a magnetic field, light irradiation or a temperature change. The aim of this work was to synthesize nano-objects of these cyanide bridged networks and to study the size reduction effect on their magnetic properties. Thus, photomagnetic octacyanometallate-based network s nanoparticles were prepared by electrostatic stabilization in water and the preparation of core-shell particles enabled a control over the size and composition of these compounds at the nanoscale. Some nano-objects were isolated in different processings (as powders, in polymers or as Langmuir-Blodgett films) and studied by various techniques (magnetic measurements by SQUID, X-ray absorption spectroscopy) to improve the photomagnetic properties and facilitate the understanding of the photo-transformation. Spin cross-over nanoparticles of the Hoffman-like FePzM(CN)4 (M=Pt, Ni ; Pz=pyrazine) were also obtained, by microemulsion, and the size reduction induces drastic changes in the spin cross-over properties. Another aim of the work was to control the grafting of a monolayer of magnetic nanoparticles on silicon. Superparamagnetic CsNiCr(CN)6 nanoparticles were strongly bonded to a mixed monolayer on a silicon substrate, without being affected by the grafting.ORSAY-PARIS 11-BU Sciences (914712101) / SudocSudocFranceF

Experimental observation of the role of countercations on the electrical conductance of Preyssler-type polyoxometalate nanodevices

Polyoxometalates are nanoscale molecular oxides with promising properties that are currently explored for molecule-based memory devices. In this work, we synthesize a series of Preyssler polyoxometalates (POMs), (Na-P5W30O110)14-,stabilized with four different counterions, H+, K+, NH4+ and tetrabutylammonium (TBA+), and we study the electron transport properties at the nanoscale (conductive atomic force microscopy, C-AFM) of molecular junctions formed by self-assembled monolayers (SAMs) of POMs electrostatically deposited on ultraflat gold surface prefunctionalized with a positively charged SAM of amine-terminated alkylthiol chains. We report that the electron transport properties of P5W30-based molecular junctions depend on the nature of the counterions, the low-bias current (in the voltage range -0.6 V to 0.6 V) gradually increasing by a factor ca. 100 by changing the counterion in the order K+, NH4+, H+ and TBA+. From a statistical study (hundreds of current-voltage traces) using a simple analytical model for charge transport in nanoscale devices, we show that the energy position of the lowest unoccupied molecular orbital (LUMO) of the P5W30 with respect of the Fermi energy of the electrodes increases from ca. 0.4 eV to 0.7 eV and that that electrode coupling energy also increases from ca. 0.05 to 1 meV in the same order from K+, NH4+, H+ to TBA+. We discuss several hypotheses on the possible origin of these features, such as a counterion-dependent dipole at the POM/electrode interface and counterion-modulated molecule/electrode hybridization, with, in both cases, the largest effect in the case of TBA+ counterions.Comment: Preprint: full text, figures and supporting informatio

Thinking Quantitatively of RNA-Based Information Transfer via Extracellular Vesicles: Lessons to Learn for the Design of RNA-Loaded EVs

Extracellular vesicles (EVs) are 50–1000 nm vesicles secreted by virtually any cell type in the body. They are expected to transfer information from one cell or tissue to another in a short- or long-distance way. RNA-based transfer of information via EVs at long distances is an interesting well-worn hypothesis which is ~15 years old. We review from a quantitative point of view the different facets of this hypothesis, ranging from natural RNA loading in EVs, EV pharmacokinetic modeling, EV targeting, endosomal escape and RNA delivery efficiency. Despite the unique intracellular delivery properties endowed by EVs, we show that the transfer of RNA naturally present in EVs might be limited in a physiological context and discuss the lessons we can learn from this example to design efficient RNA-loaded engineered EVs for biotherapies. We also discuss other potential EV mediated information transfer mechanisms, among which are ligand–receptor mechanisms

High-Quality Metal-Organic Framework Ultrathin Films for Electronically Active Interfaces.

Currently available methodologies arguably lack the exquisite control required for producing metal-organic framework (MOF) thin films of sufficient quality for electronic applications. By directing MOF transfer with self-assembled monolayers (SAMs), we achieve very smooth, homogeneous, highly oriented, ultrathin films across millimeter-scale areas that display moderate conductivity likely due to electron hopping. Here, the SAM is key for directing the transfer thereby enlarging the number and nature of the substrates of choice. We have exploited this versatility to evolve from deposition onto standard Si and Au to nonconventional substrates such as ferromagnetic Permalloy. We believe that this strategy might be useful for the integration of MOFs as active interfaces in electronic devices