Iron Oxide/Polymer Core-Shell Nanomaterials with Star-like Behavior.

Embedding nanoparticles (NPs) with organic shells is a way to control their aggregation behavior. Using polymers allows reaching relatively high shell thicknesses but suffers from the difficulty of obtaining regular hybrid objects at gram scale. Here, we describe a three-step synthesis in which multi-gram NP batches are first obtained by thermal decomposition, prior to their covalent grafting by an atom transfer radical polymerization (ATRP) initiator and to the controlled growing of the polymer shell. Specifically, non-aggregated iron oxide NPs with a core principally composed of γ-Fe2O3 (maghemite) and either polystyrene (PS) or polymethyl methacrylate (PMMA) shell were elaborated. The oxide cores of about 13 nm diameter were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). After the polymerization, the overall diameter reached 60 nm, as shown by small-angle neutron scattering (SANS). The behavior in solution as well as rheological properties in the molten state of the polymeric shell resemble those of star polymers. Strategies to further improve the screening of NP cores with the polymer shells are discussed.

Macrophage functionality and homeostasis in response to oligoethyleneglycol-coated IONPs: Impact of a dendritic architecture.

The engineering of iron oxide nanoparticles (IONPs) for biomedical use has received great interest over the past decade. In the present study we investigated the biocompatibility of IONPs grafted with linear (2P) or generation 1 (2PG1) or 2 (2PG2) dendronized oligoethyleneglycol units in THP-1-derived macrophages. To evaluate IONP effects on cell functionality and homeostasis, mitochondrial function (MTT assay), membrane permeability (LDH release), inflammation (IL-8), oxidative stress (reduced glutathione, GSH), NLRP3 inflammasome activation (IL-1ß) and nanoparticle cellular uptake (intracellular iron content) were quantified after a 4-h or 24-h cell exposure to increasing IONP concentrations (0-300 µg Fe/mL). IONPs coated with a linear molecule, NP10COP@2P, were highly taken up by cells and induced significant dose-dependent IL-8 release, oxidative stress and NLRP3 inflammasome activation. In comparison, IONPs coated with dendrons of generation 1 (NP10COP@2PG1) and 2 (NP10COP@2PG2) exhibited better biocompatibility. Effect of the dendritic architecture of the surface coating was investigated in a kinetic experiment involving cell short-term exposure (30 min or 1 h 30) to the two dendronized IONPs. NP10COP@2PG2 disrupted cellular homeostasis (LDH release, IL-1ß and IL-8 secretion) to a greater extend than NP10COP@2PG1, which makes this last IONP the best candidate as MRI contrast or theranostic agent.

Novel Alkali Activation of Titanium Substrates To Grow Thick and Covalently Bound PMMA Layers.

Titanium (Ti) is the most widely used metal in biomedical applications because of its biocompatibility; however, the significant difference in the mechanical properties between Ti and the surrounding tissues results in stress shielding which is detrimental for load-bearing tissues. In the current study, to attenuate the stress shielding effect, a new processing route was developed. It aimed at growing thick poly(methyl methacrylate) (PMMA) layers grafted on Ti substrates to incorporate a polymer component on Ti implants. However, the currently available methods do not allow the development of thick polymeric layers, reducing significantly their potential uses. The proposed route consists of an alkali activation of Ti substrates followed by a surface-initiated atom transfer radical polymerization using a phosphonic acid derivative as a coupling agent and a polymerization initiator and malononitrile as a polymerization activator. The average thickness of the grown PMMA layers is approximately 1.9 µm. The Ti activation-performed in a NaOH solution-leads to a porous sodium titanate interlayer with a hierarchical structure and an open microporosity. It promotes the covalent grafting reaction because of high hydroxyl groups' content and enables establishing a further mechanical interlocking between the growing PMMA layer and the Ti substrate. As a result, the produced graduated structure possesses high Ti/PMMA adhesion strength (∼260 MPa). Moreover, the PMMA layer is (i) thicker compared to those obtained with the previously reported techniques (∼1.9 µm), (ii) stable in a simulated body fluid solution, and (iii) biocompatible. This strategy opens new opportunities toward hybrid prosthesis with adjustable mechanical properties with respect to host bone properties for personalized medicines.

Incorporation of negatively charged iron oxide nanoparticles in the shell of anionic surfactant-stabilized microbubbles: The effect of NaCl concentration.

We report on the key effect of NaCl for the stabilization of nanoparticle-decorated microbubbles coated by an anionic perfluoroalkylated phosphate C10F21(CH2)2OP(O)(OH)2 surfactant and negatively charged iron oxide nanoparticles. We show that hollow microspheres with shells of 100-200 nm in thickness can be stabilized even at high pH when a strong ionic force is required to screen the negative charges. Due to the more drastic conditions required to stabilize the hollow microspheres, they appear to be stable enough to be deposited on a surface and dried. That can be a simple way to fabricate porous ceramics.

Stable Small Composite Microbubbles Decorated with Magnetite Nanoparticles - A Synergistic Effect between Surfactant Molecules and Nanoparticles.

Three approaches to preparing iron oxide nanoparticle-decorated microbubbles (NP-decoMBs) have been investigated. The size and stability characteristics of these microbubbles (MBs) were investigated by optical microscopy, laser light scattering and an acoustical method, and compared with those of non-decorated MBs. First, magnetite nanoparticles (Fe3O4NPs) grafted with dimyristoylphosphatidylcholine (DMPC) were synthesized and used to prepare MBs by brief sonication under an atmosphere of air saturated with perfluorohexane. These MBs had a rather large mean radius (r ~ 12 µm), and a moderate volume of encapsulated gas. Remarkably, a second approach that consisted of dispersing unbound DMPC molecules in the aqueous phase along with DMPC-grafted Fe3O4NPs prior to sonication was found to drastically change the situation, allowing the obtaining of monomodal populations of much smaller (r ~ 0.6 µm) NP-decoMBs. The latter were echogenic and stable for at least 10 days at room temperature, without significant variation of their size characteristics. In a third approach, NP-decoMBs were directly prepared from dispersions of naked Fe3O4NPs in the presence of DMPC. The resulting NP-decoMBs suspensions consisted of broadly distributed bubble populations mostly containing two populations (with r ~ 5 and ~ 15 µm). Control microbubbles made of DMPC only were small (r ~ 1.3 µm), although not as small as those formed from DMPC-grafted Fe3O4NPs in the presence of free DMPC, and were less stable, with a room temperature half-life of only ~1 day. These observations imply that there is a synergy between the Fe3O4NPs and the DMPC molecules in the air/water interfacial film stabilization process.

A new zinc hydroxy acetate hydrogen carbonate lamellar phase for growing large and clean ZnO nanorod arrays.

A novel zinc hydroxy acetate hydrogen carbonate Zn5(OH)8.2(CH3COO)(HCO3)0.8·1.9H2O, isomorphous to Zn5(OH)8(CH3COO)2·xH2O, has been obtained by the reaction of zinc acetate dihydrate in aged ethylenediamine. This phase allows the growth of large arrays of oriented and crystallized nanorods up to 8 µm in length on a substrate, without crystallization of additional particles.

Hollow magnetic microspheres obtained by nanoparticle adsorption on surfactant stabilized microbubbles.

We report on the stabilization of nanoparticle-decorated microbubbles for long periods of time using a synergism between a soluble surfactant and nanoparticles. The soluble surfactant is the perfluoroalkyl phosphate C8F17(CH2)2OP(O)(OH)2 (labeled F8H2Phos) and the nanoparticles (NPs) are 20-25 nm cobalt ferrite (CoFe2O4). The NP-F8H2Phos system has been studied by dynamic light scattering, dynamic magnetic susceptibility measurements and thermal gravimetric analysis. Microbubbles with diameters in the 1-20 µm range have been stabilized in 0.1 M NaCl brine. Its presence is crucial for the long-term stabilization. The surfactant adsorbs rapidly on bubbles and slows down the bubble shrinkage. Thus, the NPs can attach to the bubble and form a hollow sphere with a rigid shell. The charge screening by NaCl favors the attachment of NPs to the bubble surface. The coverage of the bubbles by the CoFe2O4 nanoparticle layer is confirmed by thermally induced inflation-deflation experiments and the control of bubbles with a magnetic field.

Super-elastic air/water interfacial films self-assembled from soluble surfactants.

We show that water-soluble monosodic salts of F-alkyl phosphates C(n)F(2n+1) (CH2)2OP(O)(OH)2, with n=8 and 10 (F8H2Phos and F10H2Phos) form Gibbs films with exceptionally high dilational viscoelastic modules E that reach ~900 mN m(-1) in the condensed phases. These E values are up to one order of magnitude larger than those recorded for phospholipid, protein and polymer films commonly considered as highly viscoelastic. F8H2Phos.1Na undergoes a transition between a liquid-expanded and a liquid-condensed phase. In the case of F10H2Phos.1Na, a transition occurs between a gas phase of surface domains, in which the molecules are densely packed, and a liquid-condensed phase.

pH-controlled microbubble shell formation and stabilization.

We report on microbubbles with a shell self-assembled from an anionic perfluoroalkylated surfactant, perfluorooctyl(ethyl)phosphate (F8H2Phos). Microbubbles were formed and effectively stabilized from aqueous solutions of F8H2Phos at pH 5.6-8.5. This range overlaps the domains of existence of the monosodic and disodic salts. The shell morphology of microbubbles formed spontaneously by heating aqueous solutions of F8H2Phos was monitored during cooling, directly on the microscope's stage. At pH 5.6, the shell collapses through nucleation of folds, as typical for insoluble surfactants. At pH 8.5, no folds were seen during shrinking. At higher pH, the microbubbles rapidly adsorb on the glass. The effect of pH (from 5.6 to 9.7) on adsorption kinetics of F8H2Phos at the air/water interface, and on the elasticity of its Gibbs films, was determined. At low pH, F8H2Phos is highly surface active. The interfacial film undergoes a dilute-to-condensed phase transition and a dramatic increase of elastic module, leading to extremely high values (up to 500 mN m(-1)). At high pH, the surfactant's adsorption is quasi-instantaneous, but interfacial tension lowering is limited, leading to very low elastic module (∼5 mN m(-1)). At pH 5.6 and 8.5, the interfacial tension of F8H2Phos adsorbed on millimetric bubbles and compressed at a rate similar to that exerted on micrometric bubbles during deflation is lower than the equilibrium interfacial tension. Langmuir monolayers of F8H2Phos are highly stable at low pH and feature a liquid expanded/liquid condensed transition; at high pH, they do not withstand compression. Both mono- and disodic F8H2Phos salts are needed to effectively stabilize microbubbles: the rapidly adsorbed disodic salt stabilizes a newly created air/water interface; the more surface active monosodic salt then replaces the more water-soluble disodic salt at the interface. During deflation, the surfactant shell undergoes a transition toward a highly elastic phase, which further contributes to bubble stabilization.

Nanoparticles for imaging, sensing, and therapeutic intervention.

Nanoparticles have the potential to contribute to new modalities in molecular imaging and sensing as well as in therapeutic interventions. In this Nano Focus article, we identify some of the current challenges and knowledge gaps that need to be confronted to accelerate the developments of various applications. Using specific examples, we journey from the characterization of these complex hybrid nanomaterials; continue with surface design and (bio)physicochemical properties, their fate in biological media and cells, and their potential for cancer treatment; and finally reflect on the role of animal models to predict their behavior in humans.

Alternative technique for calcium phosphate coating on titanium alloy implants.

As an alternative technique for calcium phosphate coating on titanium alloys, we propose to functionalize the metal surface with anionic bath containing chlorides of palladium or silver as activators. This new deposition route has several advantages such as controlled conditions, applicability to complex shapes, no adverse effect of heating, and cost effectiveness. A mixture of hydroxyapatite and calcium phosphate hydrate is deposited on the surface of Ti-6Al-4V. Calcium phosphate coating is built faster compared with the one by Simulated Body Fluid. Cell morphology and density are comparable to the control one; and the results prove no toxic compound is released into the medium during the previous seven days of immersion. Moreover, the cell viability is comparable with cells cultivated with the virgin medium. These experimental treatments allowed producing cytocompatible materials potentially applicable to manufacture implantable devices for orthopedic and oral surgeries.

Effect of ball-milling and Fe-/Al-doping on the structural aspect and visible light photocatalytic activity of TiO2 towards Escherichia coli bacteria abatement.

Escherichia coli abatement was studied in liquid phase under visible light in the presence of two commercial titania photocatalysts, and of Fe- and Al-doped titania samples prepared by high energy ball-milling. The two commercial titania photocatalysts, Aeroxide P25 (Evonik industries) exhibiting both rutile and anatase structures and MPT625 (Ishihara Sangyo Kaisha), a Fe-, Al-, P- and S-doped titania exhibiting only the rutile phase, are active suggesting that neither the structure nor the doping is the driving parameter. Although the MPT625 UV-visible spectrum is shifted towards the visible domain with respect to the P25 one, the effect on bacteria is not increased. On the other hand, the ball milled iron-doped P25 samples exhibit low activities in bacteria abatement under visible light due to charge recombinations unfavorable to catalysis as shown by photoluminescence measurements. While doping elements are in interstitial positions within the rutile structure in MPT625 sample, they are located at the surface in ball milled samples and in isolated octahedral units according to (57)Fe Mössbauer spectrometry. The location of doping elements at the surface is suggested to be responsible for the sample cytotoxicity observed in the dark.

Dendronized iron oxide nanoparticles for multimodal imaging.

The synthesis of small-size dendrons and their grafting at the surface of iron oxide nanoparticles were achieved with the double objective to obtain a good colloidal stability with a mean hydrodynamic diameter smaller than 100 nm and to ensure the possibility of tuning the organic coating characteristics including morphology, functionalities, physico-chemical properties, grafting of fluorescent or targeting molecules. Magnetic resonance and fluorescence imaging are then demonstrated to be simultaneously possible using such versatile superparamagnetic iron oxide nanocrystals covered by a dendritic shell displaying either carboxylate or ammonium groups at their periphery which could be further labelled with a fluorescent dye. The grafting conditions of these functionalized dendrons at the surface of SPIO NPs synthesized by co-precipitation have been optimized as a function of the nature of the peripheral functional group. The colloidal stability has been investigated in water and osmolar media, and in vitro and in vivo MRI and optical imaging measurements have been performed showing encouraging biodistribution.

Dendronized iron oxide nanoparticles as contrast agents for MRI.

Covalent attachment, through a phosphonate anchor, of hydrophilic pegylated dendrons on iron oxide nanoparticles results in versatile, robust, and highly relaxing MRI contrast agents.

Formation of ferrimagnetic films with functionalized magnetite nanoparticles using the Langmuir-Blodgett technique.

The formation of ferrimagnetic films of 39 nm magnetite nanoparticles functionalized by stilbene derivatives has been studied using the Langmuir-Blodgett technique. The stilbene moieties are grafted to the particles either via a phosphonate or a carboxylate group; in both cases the nanoparticles display similar isotherms although the microscopic initial and final states of the films are different. Two different mechanisms of film formation are proposed, based on the inorganic-organic bond stability.