Exohedral M-C-60 and M-2-C-60 (M = Pt, Pd) systems as tunable-gap building blocks for nanoarchitecture and nanocatalysis

Transition metal-fullerenes complexes with metal atoms bound on the external surface of C-60 are promising building blocks for next-generation fuel cells and catalysts. Yet, at variance with endohedral M@C-60, they have received a limited attention. By resorting to first principles simulations, we elucidate structural and electronic properties for the Pd-C-60, Pt-C-60, PtPd-C-60, Pd-2-C-60, and Pt-2-C-60 complexes. The most stable structures feature the metal atom located above a high electron density site, namely, the pi bond between two adjacent hexagons (pi-66 bond). When two metal atoms are added, the most stable configuration is those in which metal atoms still stand on p-66 bonds but tends to clusterize. The electronic structure, rationalized in terms of localized Wannier functions, provides a clear picture of the underlying interactions responsible for the stability or instability of the complexes, showing a strict relationship between structure and electronic gap

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

Interfacial Behavior of Oligo(Ethylene Glycol) Dendrons Spread Alone and in Combination with a Phospholipid as Langmuir Monolayers at the Air/Water Interface

Dendrons consisting of two phosphonate functions and three oligo(ethylene glycol) (OEG) chains grafted on a central phenoxyethylcarbamoylphenoxy group were synthesized and investigated as Langmuir monolayers at the surface of water. The OEG chain in the para position was grafted with a t-Bu end-group, a hydrocarbon chain, or a partially fluorinated chain. These dendrons are models of structurally related OEG dendrons that were found to significantly improve the stability of aqueous dispersions of iron oxide nanoparticles when grafted on their surface. Compression isotherms showed that all OEG dendrons formed liquid-expanded Langmuir monolayers at large molecular areas. Further compression led to a transition ascribed to the solubilization of the OEG chains in the aqueous phase. Brewster angle microscopy (BAM) provided evidence that the dendrons fitted with hydrocarbon chains formed liquid-expanded monolayers throughout compression, whilst those fitted with fluorinated end-groups formed crystalline-like domains, even at large molecular areas. Dimyristoylphosphatidylcholine and dendron molecules were partially miscible in monolayers. The deviations to ideality were larger for the dendrons fitted with a fluorocarbon end-group chain than for those fitted with a hydrocarbon chain. Brewster angle microscopy and atomic force microscopy supported the view that the dendrons were ejected from the phospholipid monolayer during the OEG conformational transition and formed crystalline domains on the surface of the monolayer

How a grafting anchor influences cellular uptake and in vivo fate of dendronized iron oxide nanoparticles

peer reviewe

Dendrimers toward translational nanotherapeutics: concise key step analysis

The goal of nanomedicine is to address specific clinical problems optimally, to fight human diseases, and to find clinical relevance to change clinical practice. Nanomedicine is poised to revolutionize medicine via the development of more precise diagnostic and therapeutic tools. The field of nanomedicine encompasses numerous features and therapeutic disciplines. A plethora of nanomolecular structures have been engineered and developed for therapeutic applications based on their multitasking abilities and the wide functionalization of their core scaffolds and surface groups. Within nanoparticles used for nanomedicine, dendrimers as well polymers have demonstrated strong potential as nanocarriers, therapeutic agents, and imaging contrast agents. In this review, we present and discuss the different criteria and parameters to be addressed to prepare and develop druggable nanoparticles in general and dendrimers in particular. We also describe the major requirements, included in the preclinical and clinical roadmap, for NPs/dendrimers for the preclinical stage to commercialization. Ultimately, we raise the clinical translation of new nanomedicine issues.info:eu-repo/semantics/publishedVersio

Microbubbles decorated with dendronized magnetic nanoparticles for biomedical imaging: effective stabilization via fluorous interactions

Dendrons fitted with three oligo(ethylene glycol) (OEG) chains, one of which contains a fluorinated or hydrogenated end group and bears a bisphosphonate polar head (C(n)X(2n+1)OEG(8)Den, X = F or H; n = 2 or 4), were synthesized and grafted on the surface of iron oxide nanoparticles (IONPs) for microbubble-mediated imaging and therapeutic purposes. The size and stability of the dendronized IONPs (IONP@C(n)X(2n+1)OEG(8)Den) in aqueous dispersions were monitored by dynamic light scattering. The investigation of the spontaneous adsorption of IONP@C(n)X(2n+1)OEG(8)Den at the interface between air or air saturated with perfluorohexane and an aqueous phase establishes that exposure to the fluorocarbon gas markedly increases the rate of adsorption of the dendronized IONPs to the gas/water interface and decreases the equilibrium interfacial tension. This suggests that fluorous interactions are at play between the supernatant fluorocarbon gas and the fluorinated end groups of the dendrons. Furthermore, small perfluorohexane-stabilized microbubbles (MBs) with a dipalmitoylphosphatidylcholine (DPPC) shell that incorporates IONP@C(n)X(2n+1)OEG(8)Den (DPPC/Fe molar ratio 28:1) were prepared and subsequently characterized using both optical microscopy and an acoustical method of size determination. The dendrons fitted with fluorinated end groups lead to smaller and more stable MBs than those fitted with hydrogenated groups. The most effective result is already obtained with C2F5, for which MBs of approximate to 1.0 mu m in radius reach a half-life of approximate to 6.0 h. An atomic force microscopy investigation of spin-coated mixed films of DPPC/IONP@C(2)X(5)OEG(8)Den combinations (molar ratio 28:1) shows that the IONPs grafted with the fluorinated dendrons are located within the phospholipid film, while those grafted with the hydrocarbon dendrons are located at the surface of the phospholipid film

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

Dendron based antifouling, MRI and magnetic hyperthermia properties of different shaped iron oxide nanoparticles

peer reviewe

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

Unveiling the role of surface, size, shape and defects for theranostic applications of iron oxide nanoparticles

peer reviewedNANOPARTICULES D'OXYDE DE FER OU DE MANGANÈSE DENDRONISÉES POUR L'IRM - Fédération Wallonie Bruxelle