Reorientation kinetics of superparamagnetic nanostructured rods

The attractive interactions between oppositely charged species (colloids, macromolecules etc) dispersed in water are strong, and the direct mixing of solutions containing such species generally yields to a precipitation, or to a phase separation. We have recently developed means to control the electrostatically-driven attractions between nanoparticles and polymers in water, and at the same time to preserve the stability of the dispersions. We give here an account of the formation of supracolloidal aggregates obtained by co-assembly of 7 nm particles with copolymers. Nanostructured rods of length comprised between 5 and 50 microns and diameter 500 nm were investigated. By application of a magnetic field, the rods were found to reorient along with the magnetic field lines. The kinetics of reorientation was investigated using step changes of the magnetic field of amplitude 90 degrees. From the various results obtained, among which an exponential decay of the tangent of the angle made between the rod and the field, we concluded that the rods are superparamagnetic.Comment: 12 pages - 452kB 7 - figures - 1 Table will be published in Journal of Physics : Condensed Matte

Electrosteric enhanced stability of functional sub-10 nm cerium and iron oxide particles in cell culture medium

Applications of nanoparticles in biology require that the nanoparticles remain stable in solutions containing high concentrations of proteins and salts, as well as in cell culture media. In this work, we developed simple protocols for the coating of sub-10 nm nanoparticles and evaluated the colloidal stability of dispersions in various environments. Ligands (citric acid), oligomers (phosphonate-terminated poly(ethylene oxide)) and polymers (poly(acrylic acid)) were used as nanometer-thick adlayers for cerium (CeO2) and iron (gamma-Fe2O3) oxide nanoparticles. The organic functionalities were adsorbed on the particle surfaces via physical (electrostatic) forces. Stability assays at high ionic strength and in cell culture media were performed by static and dynamic light scattering. Among the three coating examined, we found that only poly(acrylic acid) fully preserved the dispersion stability on the long term (> weeks). The improved stability was explained by the multi-point attachments of the chains onto the particle surface, and by the adlayer-mediated electrosteric interactions. These results suggest that anionically charged polymers represent an effective alternative to conventional coating agents.Comment: 8 figures, 10 pages, 4 tables. to appear in Langmui

Delayed hepatic uptake of multi-phosphonic acid poly(ethylene glycol) coated iron oxide measured by real-time Magnetic Resonance Imaging

We report on the synthesis, characterization, stability and pharmacokinetics of novel iron based contrast agents for magnetic resonance imaging (MRI). Statistical copolymers combining multiple phosphonic acid groups and poly(ethylene glycol) (PEG) were synthesized and used as coating agents for 10 nm iron oxide nanocrystals. In vitro, protein corona and stability assays show that phosphonic acid PEG copolymers outperform all other coating types examined, including low molecular weight anionic ligands and polymers. In vivo, the particle pharmacokinetics is investigated by monitoring the MRI signal intensity from mouse liver, spleen and arteries as a function of the time, between one minute and seven days after injection. Iron oxide particles coated with multi-phosphonic acid PEG polymers are shown to have a blood circulation lifetime of 250 minutes, i.e. 10 to 50 times greater than that of recently published PEGylated probes and benchmarks. The clearance from the liver takes in average 2 to 3 days and is independent of the core size, coating and particle stability. By comparing identical core particles with different coatings, we are able to determine the optimum conditions for stealth MRI probes.Comment: 19 pages 8 figures, RSC Advances, 201

Intracellular micro-rheology probed by micron-sized wires

In the last decade, rapid advances have been made in the field of micro-rheology of cells and tissues. Given the complexity of living systems, there is a need for the development of new types of nano- and micron-sized probes, and in particular of probes with controlled interactions with the surrounding medium. In the present paper, we evaluate the use of micron-sized wires as potential probes of the mechanical properties of cells. The wire-based micro-rheology technique is applied to living cells such as murine fibroblasts and canine kidney epithelial cells. The mean-squared angular displacement (MSAD) of wires associated to their rotational dynamics is obtained as a function of the time using optical microscopy and image processing. It reveals a Brownian-like diffusive regime where the MSA scale linearly with time and as the inverse of the cube of the wire length. This scaling suggests that an effective viscosity of the intracellular medium can be determined, and that in the range 1 - 10 micrometers it does not depend on the length scale over which it is measured.Comment: 13 page, 5 figures, accepted at Biomaterial

Linear and nonlinear rheology of wormlike micelles

Several surfactant molecules self-assemble in solution to form long, cylindrical, flexible wormlike micelles. These micelles can be entangled with each other leading to viscoelastic phases. The rheological properties of such phases are very interesting and have been the subject of a large number of experimental and theoretical studies in recent years. We shall report on our recent work on the macrorheology, microrheology and nonlinear flow behaviour of dilute aqueous solutions of a surfactant CTAT (Cetyltrimethylammonium Tosilate). This system forms elongated micelles and exhibits strong viscoelasticity at low concentrations ($\sim$ 0.9 wt%) without the addition of electrolytes. Microrheology measurements of $G(\omega)$ have been done using diffusing wave spectroscopy which will be compared with the conventional frequency sweep measurements done using a cone and plate rheometer. The second part of the paper deals with the nonlinear rheology where the measured shear stress $\sigma$ is a nonmonotonic function of the shear rate $\dot{\gamma}$. In stress-controlled experiments, the shear stress shows a plateau for $\dot{\gamma}$ larger than some critical strain rate, similar to the earlier reports on CPyCl/NaSal system. Cates et al have proposed that the plateau is a signature of mechanical instability in the form of shear bands. We have carried out extensive experiments under controlled strain rate conditions, to study the time-dependence of shear stress. The measured time series of shear stress has been analysed in terms of correlation integrals and Lyapunov exponents to show unambiguously that the behaviour is typical of low dimensional dynamical systems.Comment: 15 pages, 10 eps figure

Universal scattering behavior of co-assembled nanoparticle-polymer clusters

Water-soluble clusters made from 7 nm inorganic nanoparticles have been investigated by small-angle neutron scattering. The internal structure factor of the clusters was derived and exhibited a universal behavior as evidenced by a correlation hole at intermediate wave-vectors. Reverse Monte-Carlo calculations were performed to adjust the data and provided an accurate description of the clusters in terms of interparticle distance and volume fraction. Additional parameters influencing the microstructure were also investigated, including the nature and thickness of the nanoparticle adlayer.Comment: 5 pages, 4 figures, paper published in Physical Review

Electrostatic co-assembly of iron oxide nanoparticles and polymers : towards the generation of highly persistent superparamagnetic nanorods

A paradigm proposed recently by Boal et al. (A.K. Boal et al., Nature 404, 746-748, 2000) deals with the possibility to use inorganic nanoparticles as building blocks for the design and fabrication of colloidal and supracolloidal assemblies. It is anticipated that these constructs could be made of different shapes, patterns and functionalities and could constitute the components of future nanodevices including sensors, actuators or nanocircuits. Here we report a protocol that allowed us to fabricate such nanoparticle aggregates. The building blocks of the constructs were anionically coated iron oxide nanocrytals (superparamagnetic, size 7 nm) and cationic-neutral block copolymers. We have shown that the electrostatic interactions between charged species can be controlled by tuning the ionic strength of the dispersion. Under appropriate conditions, the control of electrostatics resulted in the elaboration of spherical or elongated aggregates at the micrometer length scale. The elongated aggregates were found to be rod-like, with diameters of a few hundred nanometers and lengths between 1 and 50 micrometers. In addition to their remarkable stiffness, the nanostructured rods were found to reorient along with an externally applied magnetic field, in agreement with the laws of superparamagnetism.Comment: 6 pages, 5 figures, appeared in Advanced materials in September 2008, reference

Loss of solutions in shear banding fluids in shear banding fluids driven by second normal stress differences

Edge fracture occurs frequently in non-Newtonian fluids. A similar instability has often been reported at the free surface of fluids undergoing shear banding, and leads to expulsion of the sample. In this paper the distortion of the free surface of such a shear banding fluid is calculated by balancing the surface tension against the second normal stresses induced in the two shear bands, and simultaneously requiring a continuous and smooth meniscus. We show that wormlike micelles typically retain meniscus integrity when shear banding, but in some cases can lose integrity for a range of average applied shear rates during which one expects shear banding. This meniscus fracture would lead to ejection of the sample as the shear banding region is swept through. We further show that entangled polymer solutions are expected to display a propensity for fracture, because of their much larger second normal stresses. These calculations are consistent with available data in the literature. We also estimate the meniscus distortion of a three band configuration, as has been observed in some wormlike micellar solutions in a cone and plate geometry.Comment: 23 pages, to be published in Journal of Rheolog

Dynamic Response of Block Copolymer Wormlike Micelles to Shear Flow

The linear and non-linear dynamic response to an oscillatory shear flow of giant wormlike micelles consisting of Pb-Peo block copolymers is studied by means of Fourier transform rheology. Experiments are performed in the vicinity of the isotropic-nematic phase transition concentration, where the location of isotropic-nematic phase transition lines is determined independently. Strong shear-thinning behaviour is observed due to critical slowing down of orientational diffusion as a result of the vicinity of the isotropic- nematic spinodal. This severe shear-thinning behaviour is shown to result in gradient shear banding. Time-resolved Small angle neutron scattering experiments are used to obtain insight in the microscopic phenomena that underly the observed rheological response. An equation of motion for the order-parameter tensor and an expression of the stress tensor in terms of the order-parameter tensor are used to interpret the experimental data, both in the linear and non-linear regime. Scaling of the dynamic behaviour of the orientational order parameter and the stress is found when critical slowing down due to the vicinity of the isotropic-nematic spinodal is accounted for.Comment: Accepted by J. Phys.: Condens. Matter, CODEF II Special Issue. 20 pages, 9 figure

Dynamic Response of Block Copolymer Wormlike Micelles to Shear Flow

The linear and non-linear dynamic response to an oscillatory shear flow of giant wormlike micelles consisting of Pb-Peo block copolymers is studied by means of Fourier transform rheology. Experiments are performed in the vicinity of the isotropic-nematic phase transition concentration, where the location of isotropic-nematic phase transition lines is determined independently. Strong shear-thinning behaviour is observed due to critical slowing down of orientational diffusion as a result of the vicinity of the isotropic- nematic spinodal. This severe shear-thinning behaviour is shown to result in gradient shear banding. Time-resolved Small angle neutron scattering experiments are used to obtain insight in the microscopic phenomena that underly the observed rheological response. An equation of motion for the order-parameter tensor and an expression of the stress tensor in terms of the order-parameter tensor are used to interpret the experimental data, both in the linear and non-linear regime. Scaling of the dynamic behaviour of the orientational order parameter and the stress is found when critical slowing down due to the vicinity of the isotropic-nematic spinodal is accounted for.Comment: Accepted by J. Phys.: Condens. Matter, CODEF II Special Issue. 20 pages, 9 figure