When polyelectrolyte-neutral block copolymers are mixed in aqueous solutions with oppositely charged species, stable complexes are found to form spontaneously. The mechanism is based on electrostatics and on the compensation between the opposite charges. Electrostatic complexes exhibit a core-shell microstructure. In the core, the polyelectrolyte blocks and the oppositely charged species are tightly bound and form a dense coacervate microphase. The shell is made of the neutral chains and surrounds the core. In this paper, we report on the structural and magnetic properties of such complexes made from 6.3 nm diameter superparamagnetic nanoparticles (maghemite gamma-Fe(2)O(3)) and cationic-neutral copolymers. The copolymers investigated are poly(trimethylammonium ethylacrylate methyl sulfate)-b-poly(acrylamide), with molecular weights 5000-b-30000 g mol(-)(1) and 110000-b-30000 g mol(-)(1). The mixed copolymer-nanoparticle aggregates were characterized by a combination of light scattering and cryo-transmission electron microscopy. Their hydrodynamic diameters were found in the range 70-150 nm, and their aggregation numbers (number of nanoparticles per aggregate) from tens to hundreds. In addition, Magnetic Resonance Spin-Echo measurements show that the complexes have a better contrast in Magnetic Resonance Imaging than single nanoparticles and that these complexes could be used for biomedical applications.

No abstract

We exploit a precipitation-redispersion mechanism for complexation of short chain polyelectrolytes with cerium oxide nanoparticles to extend their stability ranges. As synthesized, cerium oxide sols at pH 1.4 consist of monodisperse cationic nanocrystalline particles having a hydrodynamic diameter of 10 nm and a molecular weight 400000 g·mol -1 . We show that short chain uncharged poly(acrylic acid) at low pH when added to a cerium oxide sols leads to macroscopic precipitation. As the pH is increased, the solution spontaneously redisperses into a clear solution of single particles with an anionic poly(acrylic acid) corona. The structure and dynamics of cerium oxide nanosols and their hybrid polymer-inorganic complexes in solution are investigated by static and dynamic light scattering, X-ray scattering, and by chemical analysis. Quantitative analysis of the redispersed sol gives rise to an estimate of 40 -50 polymer chains per particle for stable suspension. This amount represents 20 % of the mass of the polymer-nanoparticle complexes. This complexation adds utility to the otherwise unstable cerium oxide dispersions by extending the range of stability of the sols in terms of pH, ionic strength and concentration.

Magnetic particles are very efficient magnetic resonance imaging (MRI) contrast agents. In recent years, chemists have unleashed their imagination to design multi-functional nanoprobes for biomedical applications including MRI contrast enhancement. This study is focused on the direct relationship between the size and magnetization of the particles and their nuclear magnetic resonance relaxation properties, which condition their efficiency. Experimental relaxation results with maghemite particles exhibiting a wide range of sizes and magnetizations are compared to previously published data and to well-established relaxation theories with a good agreement. This allows deriving the experimental master curve of the transverse relaxivity versus particle size and to predict the MRI contrast efficiency of any type of magnetic nanoparticles. This prediction only requires the knowledge of the size of the particles impermeable to water protons and the saturation magnetization of the corresponding volume. To predict the T(2) relaxation efficiency of magnetic single crystals, the crystal size and magnetization - obtained through a single Langevin fit of a magnetization curve - is the only information needed. For contrast agents made of several magnetic cores assembled into various geometries (dilute fractal aggregates, dense spherical clusters, core-shell micelles, hollow vesicles…), one needs to know a third parameter, namely the intra-aggregate volume fraction occupied by the magnetic materials relatively to the whole (hydrodynamic) sphere. Finally a calculation of the maximum achievable relaxation effect - and the size needed to reach this maximum - is performed for different cases: maghemite single crystals and dense clusters, core-shell particles (oxide layer around a metallic core) and zinc-manganese ferrite crystals.

We report on the nonlinear mechanical response of surfactant wormlike micelles subjected to steady shear flow. The system placed under scrutiny is made of cetylpyridinium chloride, sodium salicylate, and salted water at 0.5M NaCl ͑abbreviated as CPCl-Sal͒. We have investigated solutions in the intermediate concentration ranges, at ϭ6%, 8% and ϭ12% for temperatures ranging between 20°C and 50°C. In these T and ranges, we first confirm that the present system is a true Maxwell fluid. As a consequence, the nonlinear rheology can be formulated in terms of the normalized quantities, *ϭ/G 0 and ␥ *ϭ␥ R , where G 0 is the elastic plateau modulus and R the terminal relaxation time of the Maxwell fluid. Second, we demonstrate that the flow curves of the CPCl-Sal wormlike micelles * ͑␥ *͒ are invariant with respect to relative changes in temperature and concentration. This enables us to define superimposition procedures between flow curves obtained at different temperatures and concentrations and to derive the so-called ''master dynamic phase diagram'' of the CPCl-Sal wormlike micelles. One crucial feature of this master phase diagram is the existence of a critical behavior at TϭT c . Here, the stress * levels off progressively up to a plateau that is reduced to a single flat point of coordinates ͑*ϭ0.9, ␥ *ϭ3͒. The low-temperature regime (TϽT c ) is again identified by a shear stress plateau beginning by a true discontinuity of slope in the * ͑␥ *͒ behavior. At high T ͑ϾT c ͒, * increases monotonously at all shear rates. In order to examine the state of shearing at the stress plateau, flow birefringence experiments were undertaken with a rheo-optical device working with polarized light propagating parallel to the vorticity axis of the Couette. In the plateau regime, the flow is clearly inhomogeneous. Within the gap of a cell, two phases of very different birefringence are observed in the steady state of shearing, as well as after cessation of the shearing.

We review the experimental and theoretical results obtained during the past decade on the structure and rheology of wormlike micellar solutions. We focus on the linear and nonlinear viscoelasticity and emphasize the analogies with polymers. Based on a comprehensive survey of surfactant systems, the present study shows the existence of standard rheological behaviors for semidilute and concentrated solutions. One feature of this behavior is a shear banding transition associated with a stress plateau in the nonlinear mechanical response. For concentrated solutions, we show that in the plateau region the shear bands are isotropic and nematic.

We report on the formation of colloidal complexes resulting from the electrostatic self-assembly of polyelectrolyte−neutral diblock copolymers and oppositely charged surfactant. The copolymers investigated are asymmetric and characterized by a large neutral block. Using light, neutron, and X-ray scattering experiments, we have shown that the colloidal complexes exhibit a core−shell microstructure. The core is described as a dense microphase of micelles connected by the polyelectrolyte blocks, whereas the shell is a diffuse brush made from the neutral chains. For all copolymer/surfactant systems, we show the existence of a critical charge ratio Z C (∼1) above which the formation of hierarchical structures takes place. Copolymers of different molecular weight and polyelectrolyte blocks have been studied in order to assess the analogy with another type of core−shell aggregates, the polymeric micelles made from amphiphilic copolymers. The present results indicate that the radius of the core depends essentially on the degree of polymerization of the polyelectrolyte block and not on that of the neutral chain. On the other hand, the size of the overall colloid increases with increasing molecular weights of the copolymers. Taking advantage of the resolution of X-ray scattering, we have also shown that the micelles in the core of the aggregates are structurally disordered.

Cerium oxide nanoparticles are known to catalyze the decomposition of reactive oxygen species such as the superoxide radical and hydrogen peroxide. Herein, we examine the superoxide dismutase (SOD) and catalase (CAT) mimetic catalytic activities of nanoceria and demonstrate the existence of generic behaviors. For particles of sizes 4.5, 7.8, 23 and 28 nm, the SOD and CAT catalytic activities exhibit the characteristic shape of a Langmuir isotherm as a function of cerium concentration. The results show that the catalytic effects are enhanced for smaller particles and for the particles with the largest Ce3+ fraction. The SOD-like activity obtained from the different samples is found to superimpose on a single master curve using the Ce3+ surface area concentration as a new variable, indicating the existence of particle independent redox mechanisms. For the CAT assays, the adsorption of H2O2 molecules at the particle surface modulates the efficacy of the decomposition process and must be taken into account. We design an amperometry-based experiment to evaluate the H2O2 adsorption at nanoceria surfaces, leading to the renormalization of the particle specific area. Depending on the particle type the amount of adsorbed H2O2 molecules varies from 2 to 20 nm-2. The proposed scalings are predictive and allow the determination of the SOD and CAT catalytic properties of cerium oxide solely from physicochemical features.