A 3D insight on the catalytic nanostructuration of few-layer graphene

The catalytic cutting of few-layer graphene is nowadays a hot topic in materials research due to its potential applications in the catalysis field and the graphene nanoribbons fabrication. We show here a 3D analysis of the nanostructuration of few-layer graphene by iron-based nanoparticles under hydrogen flow. The nanoparticles located at the edges or attached to the steps on the FLG sheets create trenches and tunnels with orientations, lengths and morphologies defined by the crystallography and the topography of the carbon substrate. The cross-sectional analysis of the 3D volumes highlights the role of the active nanoparticle identity on the trench size and shape, with emphasis on the topographical stability of the basal planes within the resulting trenches and channels, no matter the obstacle encountered. The actual study gives a deep insight on the impact of nanoparticles morphology and support topography on the 3D character of nanostructures built up by catalytic cutting

Polyol synthesis, functionalisation, and biocompatibility studies of superparamagnetic iron oxide nanoparticles as potential MRI contrast agents

Iron oxide nanoparticles (IONPs) of low polydispersity were obtained through a simple polyol synthesis in high pressure and high temperature conditions. The control of the size and morphology of the nanoparticles was studied by varying the solvent used, the amount of iron precursor and the reaction time. Compared with conventional synthesis methods such as thermal decomposition or co-precipitation, this process yields nanoparticles with a narrow particle size distribution in a simple, reproducible and cost effective manner without the need for an inert atmosphere. For example, IONPs with a diameter of ca. 8 nm could be made in a reproducible manner and with good crystallinity as evidenced by X-ray diffraction analysis and high saturation magnetization value (84.5 emu g(-1)). The surface of the IONPs could be tailored post synthesis with two different ligands which provided functionality and stability in water and phosphate buffer saline (PBS). Their potential as a magnetic resonance imaging (MRI) contrast agent was confirmed as they exhibited high r1 and r2 relaxivities of 7.95 mM(-1) s(-1) and 185.58 mM(-1) s(-1) respectively at 1.4 T. Biocompatibility and viability of IONPs in primary human mesenchymal stem cells (hMSCs) was studied and confirmed

Nanotrench for nano and microparticle electrical interconnects

We present a simple and versatile patterning procedure for the reliable and reproducible fabrication of high aspect ratio (10 4 ) electrical interconnects that have separation distances down to 20 nm and lengths of several hundreds of microns. The process uses standard optical lithography techniques and allows parallel processing of many junctions, making it easily scalable and industrially relevant. We demonstrate the suitability of these nanotrenches as electrical interconnects for addressing micro and nanoparticles by realizing several circuits with integrated species. Furthermore, low impedance metal-metal low contacts are shown to be obtained when trapping a single metal-coated microsphere in the gap, emphasizing the intrinsic good electrical conductivity of the interconnects, even though a wet process is used. Highly resistive magnetite-based nanoparticles networks also demonstrate the advantage of the high aspect ratio of the nanotrenches for providing access to electrical properties of highly resistive materials, with leakage current levels below 1 pA. © 2010 IOP Publishing Ltd

A detailed investigation of the onion structure of exchanged coupled magnetic Fe3-dO4@CoFe2O4@Fe3-dO4 nanoparticles

Nanoparticles that combine several magnetic phases offer wide perspectives for cutting edge applications because of the high modularity of their magnetic properties. Besides the addition of the magnetic characteristics intrinsic to each phase, the interface that results from core-shell and, further, from onion structures leads to synergistic properties such as magnetic exchange coupling. Such a phenomenon is of high interest to overcome the superparamagnetic limit of iron oxide nanoparticles which hampers potential applications such as data storage or sensors. In this manuscript, we report on the design of nanoparticles with an onion-like structure which has been scarcely reported yet. These nanoparticles consist of a Fe3-dO4 core covered by a first shell of CoFe2O4 and a second shell of Fe3-dO4, e.g., a Fe3-dO4@CoFe2O4@Fe3-dO4 onion-like structure. They were synthesized through a multistep seed-mediated growth approach which consists consists in performing three successive thermal decomposition of metal complexes in a high-boiling-point solvent (about 300 °C). Although TEM micrographs clearly show the growth of each shell from the iron oxide core, core sizes and shell thicknesses markedly differ from what is suggested by the size increasing. We investigated very precisely the structure of nanoparticles in performing high resolution (scanning) TEM imaging and geometrical phase analysis (GPA). The chemical composition and spatial distribution of atoms were studied by electron energy loss spectroscopy (EELS) mapping and spectroscopy. The chemical environment and oxidation state of cations were investigated by 57Fe Mössbauer spectrometry, soft X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The combination of these techniques allowed us to estimate the increase of Fe2+ content in the iron oxide core of the core@shell structure and the increase of the cobalt ferrite shell thickness in the core@shell@shell one, whereas the iron oxide shell appears to be much thinner than expected. Thus, the modification of the chemical composition as well as the size of the Fe3-dO4 core and the thickness of the cobalt ferrite shell have a high impact on the magnetic properties. Furthermore, the growth of the iron oxide shell also markedly modifies the magnetic properties of the core-shell nanoparticles, thus demonstrating the high potential of onion-like nanoparticles to accurately tune the magnetic properties of nanoparticles according to the desired applications. © 2021 American Chemical Society

Towards nanoprinting with metals on graphene

Graphene and carbon nanotubes are envisaged as suitable materials for the fabrication of the new generation of nanoelectronics. The controlled patterning of such nanostructures with metal nanoparticles is conditioned by the transfer between a recipient and the surface to pattern. Electromigration under the impact of an applied voltage stands at the base of printing discrete digits at the nanoscale. Here we report the use of carbon nanotubes as nanoreservoirs for iron nanoparticles transfer on few-layer graphene. An initial Joule-induced annealing is required to ensure the control of the mass transfer with the nanotube acting as a `pen' for the writing process. By applying a voltage, the tube filled with metal nanoparticles can deposit metal on the surface of the graphene sheet at precise locations. The reverse transfer of nanoparticles from the graphene surface to the nanotube when changing the voltage polarity opens the way for error corrections

Properties and suspension stability of dendronized iron oxide nanoparticles for MRI applications

Functionalized iron oxide nanoparticles have attracted an increasing interest in the last 10 years as contrast agents for MRI. One challenge is to obtain homogeneous and stable aqueous suspensions of iron oxide nanoparticles without aggregates. Iron oxide nanoparticles with sizes around 10 nm were synthesized by two methods: the particle size distribution in water suspension of iron oxide nanoparticles synthesized by the co-precipitation method was improved by a process involving two steps of ligand exchange and phase transfer and was compared with that of iron oxide nanoparticles synthesized by thermal decomposition and functionalized by the same dendritic molecule. The saturation magnetization of dendronized nanoparticles synthesized by thermal decomposition was lower than that of nanoparticles synthesized by co-precipitation. The r(2) relaxivity values were shown to decrease with the agglomeration state in suspension and high r(2) values and r(2)/r(1) ratios were obtained with nanoparticles synthesized by co-precipitation by comparison with those of commercial products. Dendronized iron oxide nanoparticles thus have potential properties as contrast agent. Copyright (C) 2010 John Wiley & Sons, Ltd

A 3D insight on the catalytic nanostructuration of few-layer graphene

The catalytic cutting of few-layer graphene is nowadays a hot topic in materials research due to its potential applications in the catalysis field and the graphene nanoribbons fabrication. We show here a 3D analysis of the nanostructuration of few-layer graphene by iron-based nanoparticles under hydrogen flow. The nanoparticles located at the edges or attached to the steps on the FLG sheets create trenches and tunnels with orientations, lengths and morphologies defined by the crystallography and the topography of the carbon substrate. The cross-sectional analysis of the 3D volumes highlights the role of the active nanoparticle identity on the trench size and shape, with emphasis on the topographical stability of the basal planes within the resulting trenches and channels, no matter the obstacle encountered. The actual study gives a deep insight on the impact of nanoparticles morphology and support topography on the 3D character of nanostructures built up by catalytic cutting

Tailored biological retention and efficient clearance of pegylated ultra-small MnO nanoparticles as positive MRI contrast agents for molecular imaging

A majority of MRI procedures requiring intravascular injections of contrast agents are performed with paramagnetic chelates. Such products induce vascular signal enhancement and they are rapidly excreted by the kidneys. Unfortunately, each chelate is made of only one paramagnetic ion, which, taken individually, has a limited impact on the MRI signal. In fact, the detection of molecular events in the nanomolar range using T-1-weighted MRI sequences requires the design of ultra-small particles containing hundreds of paramagnetic ions per contrast agent unit. Ultra-small nanoparticles of manganese oxide (MnO, 6-8 nm diameter) have been developed and proposed as an efficient and at least 1000 x more sensitive “positive” MRI contrast agent. However no evidence has been found until now that an adequate surface treatment of these particles could maintain their strong blood signal enhancement, while allowing their rapid and efficient excretion by the kidneys or by the hepatobiliairy pathway. Indeed, the sequestration of MnO particles by the reticuloendothelial system followed by strong uptake in the liver and in the spleen could potentially lead to Mn2+-induced toxicity effects. For ultra-small MnO particles to be applied in the clinics, it is necessary to develop coatings that also enable their efficient excretion within hours. This study demonstrates for the first time the possibility to use MnO particles as T-1 vascular contrast agents, while enabling the excretion of > 70% of all the Mn injected doses after 48 h. For this, small, biocompatible and highly hydrophilic pegylated bis-phosphonate dendrons (PDns) were grafted on MnO particles to confer colloidal stability, relaxometric performance, and fast excretion capacity. The chemical and colloidal stability of MnO@PDn particles were confirmed by XPS, FTIR and DLS. The relaxometric performance of MnO@PDns as “positive” MRI contrast agents was assessed (r(1) = 4.4 mM(-1) s(-1), r(2)/r(1) = 8.6; 1.41 T and 37 degrees C). Mice were injected with 1.21 mu g Mn per kg (22 mu mol Mn per kg), and scanned in MRI up to 48 h. The concentration of Mn in key organs was precisely measured by neutron activation analysis and confirmed, with MRI, the possibility to avoid RES nanoparticle sequestration through the use of phosphonate dendrons. Due to the fast kidney and hepatobiliairy clearance of MnO particles conferred by PDns, MnO nanoparticles can now be considered for promising applications in T1-weighted MRI applications requiring less toxic although highly sensitive “positive” molecular contrast agents

Efficient synthesis of small-sized phosphonated dendrons: potential organic coatings of iron oxide nanoparticles:

We report herein the synthesis of biocompatible small-sized phosphonated monomers and dendrons used as functional coatings of metal oxide nanoparticles, more specifically superparamagnetic iron oxides (SPIOs) for magnetic resonance imaging (MRI) and therapy through hyperthermia. The molecules were engineered to modulate their size, their hydrophilic and/or biocompatible character (poly(amido) amine versus oligoethyleneglycol), the number of anchoring phosphonate groups (monophosphonate versus phosphonic tweezers) and the number of peripheral functional groups for further grafting of dyes or specific vectors. Such a library of hydrophilic phosphonic acids opens new possibilities for the investigation of dendronized nanohybrids as theranostics