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Solution self-assembly of amphiphilic block copolymers (BCs) is typically performed by a solvent-to-water exchange. However, BC assemblies are often trapped in metastable states depending on the mixing conditions such as the magnitude and rate of water addition. BC self-assembly can be performed under near thermodynamic control by dialysis, which accounts for a slow and gradual water addition. In this Letter we report the use of a specifically designed dialysis cell to continuously monitor by dynamic light scattering and small-angle neutron scattering the morphological changes of PDMS-b-PEG BCs self-assemblies during THF-to-water exchange. The complete phase diagrams of near-equilibrium structures can then be established. Spherical micelles first form before evolving to rod-like micelles and vesicles, decreasing the total developed interfacial area of self-assembled structures in response to increasing interfacial energy as the water content increases. The dialysis kinetics can be tailored to the time scale of BC self-assembly by modifying the membrane pore size, which is of interest to study the interplay between thermodynamics and kinetics in self-assembly pathways.

Health concerns associated with the advent of nanotechnologies have risen sharply when it was found that particles of nanoscopic dimensions reach the cell lumina. Plasma and organelle lipid membranes, which are exposed to both the incoming and the engulfed nanoparticles, are the primary targets of possible disruptions. However, reported adhesion, invagination and embedment of nanoparticles (NPs) do not compromise the membrane integrity, precluding direct bilayer damage as a mechanism for toxicity. Here it is shown that a lipid membrane can be torn by small enough nanoparticles, thus unveiling mechanisms for how lipid membrane can be compromised by tearing from nanoparticles. Surprisingly, visualization by cryo transmission electron microscopy (cryo-TEM) of liposomes exposed to nanoparticles revealed also that liposomal laceration is prevented by particle abundance. Membrane destruction results thus from a subtle particle-membrane interplay that is here elucidated. This brings into a firmer molecular basis the theorized mechanisms of nanoparticle effects on lipid bilayers and paves the way for a better assessment of nanoparticle toxicity.

Dispersion of tubules made of diacetylenic phospholipids (DC 8,9 PC), in aqueous colloidal dispersions of magnetic nanoparticles is studied as a function of the sign of particles surface charges. In every case the tubule-vesicle transition temperature is decreased by the presence of the magnetic nanoparticles. Electrophoresis experiments on the tubules in pure water permits to conclude on a negative apparent surface charge. We study the magnetic response of the system to a static or stationary rotating field and to a magnetic field gradient. These experiments reveal an excess or a lack of magnetic permeability between tubules and the surrounding medium. Electron microscopy confirms these results showing an electrostatic interaction between the phospholipidic bilayer and the magnetic particles.

In this article, we present new samples of lamellar magnetic nanocomposites based on the self-assembly of a polystyrene-b-poly(n-butyl methacrylate) diblock copolymer synthesized by atom transfer radical polymerization. The polymer films were loaded with magnetic iron oxide nanoparticles covered with polystyrene chains grown by surface initiated-ATRP. The nanostructuration of the pure and magnetically loaded copolymer films on silicon was studied by atomic force microscopy, ellipsometry, neutron reflectivity and contact angle measurement. The present study highlights the strong influence of the copolymer extremity - driven itself by the choice of the ATRP chemical route - on the order of the repetition sequences of the blocks in the multi-lamellar films. In addition, a narrower distribution of the nanoparticles' sizes was examined as a control parameter of the SI-ATRP reaction.

A long time ago, Brochard and de Gennes predicted the possibility of significantly decreasing the critical magnetic field of the Fredericksz transition (the magnetic Fredericksz threshold) in a mixture of nematic liquid crystals and ferromagnetic particles, the so-called ferronematics. This phenomenon has rarely been measured, usually due to soft homeotropic anchoring induced at the nanoparticle surface. Here we present an optical study of the magnetic Fredericksz transition combined with a light scattering study of the classical nematic liquid crystal, 5CB, doped with 6 nm diameter magnetic and non-magnetic nanoparticles. Surprisingly, for both nanoparticles, we observe at room temperature a net decrease of the threshold field of the Fredericksz transition at low nanoparticle concentrations, which appears associated with a coating of the nanoparticles by a brush of polydimethylsiloxane copolymer chains inducing planar anchoring of the director on the nanoparticle surface. Moreover the magnetic Fredericksz threshold exhibits non-monotonic behaviour as a function of the nanoparticle concentration for both types of nanoparticles, first decreasing down to a value from 23\% to 31\% below that of pure 5CB, then increasing with a further increase of nanoparticle concentration. This is interpreted as an aggregation starting at around 0.02 weight fraction that consumes more isolated nanoparticles than those introduced when the concentration is increased above $c = 0.05$ weight fraction (volume fraction $3.5 \times 10^{-2}$). This shows the larger effect of isolated nanoparticles on the threshold with respect to aggregates. From dynamic light scattering measurements we deduced that, if the decrease of the magnetic threshold when the nanoparticle concentration increases is similar for both kinds of nanoparticles, the origin of this decrease is different for magnetic and non-magnetic nanoparticles. For non-magnetic nanoparticles, the behavior may be associated with a decrease of the elastic constant due to weak planar anchoring. For magnetic nanoparticles there are non-negligible local magnetic interactions between liquid crystal molecules and magnetic nanoparticles, leading to an increase of the average order parameter. This magnetic interaction thus favors an easier liquid crystal director rotation in the presence of external magnetic field, able to reorient the magnetic moments of the nanoparticles along with the molecules.

The polyol route is a versatile and up-scalable method to produce large batches of iron oxide nanoparticles with well-defined structure and magnetic properties. Controlling parameters such as temperature and duration of reaction, heating profile, nature of polyol solvent or of organometallic precursors were reported in previous studies of literature, but none of them described yet the crucial role of water in the forced hydrolysis pathway, whose presence is mandatory for nanoparticle production. This communication investigates the influence of the water amount and temperature at which it is injected in the reflux system for either pure polyol or mixture with a poly(hydroxy) amine. Distinct morphologies of nanoparticles were thereby obtained, from ultra-ultra-small smooth spheres down to 4 nm in diameter to large ones up to 37 nm in diameter. Nanoflowers were also synthesized, which are well-defined multi-core assemblies with narrow grain size dispersity. A diverse and large library of samples was obtained by playing on the nature of solvents and amount of water traces while keeping all the other parameters fixed. The varied morphologies lead to magnetic nanoparticles well-fitting to required applications among magnetic hyperthermia and MRI contrast agent, or both., Comment: Main text: 36 pages, 8 figures; Supporting information: 10 pages, 15 figures (including graphical abstract)

Several studies have combined heat and gravitational energy exchanges to create novel heat engines. A common theoretical framework is developed here to describe thermogravitational cycles which have the same efficiencies as the Carnot, Rankine or Brayton cycles. Considering a working fluid, enclosed in a balloon, inside a column filled with a transporting fluid, the cycle is composed of four steps. Starting from the top of the column, the balloon goes down by gravity, receives heat from a hot source at the bottom, rises and delivers heat to a cold source at the top. Unlike classic power cycles which need external work to operate the compressor, thermogravitational cycles can operate as "pure power cycle" where no external work is provided to drive the cycle. To illustrate this concept, the prototype of a thermogravitational electrical generator is presented. It uses a hot source of low temperature (average temperature near 57{\deg}C) and relies on the gravitational energy exchanges of an organic fluorinated fluid inside a balloon attached to a magnetic marble producing an electromotive force of 50 mV peak to peak by the use of a linear alternator. This heat engine is well suited to be operated using renewable energy sources such as geothermal gradients or focused sunbeams., Comment: 22 pages, 9 figures

Nowadays, magnetic hyperthermia constitutes a complementary approach to cancer treatment. The use of magnetic particles as heating mediators, proposed in the 1950s, provides a novel strategy for improving tumor treatment and, consequently, patient quality of life. This review reports a broad overview about several aspects of magnetic hyperthermia addressing new perspectives and the progress on relevant features such as the ad hoc preparation of magnetic nanoparticles, physical modeling of magnetic heating, methods to determine the heat dissipation power of magnetic colloids including the development of experimental apparatus and the influence of biological matrices on the heating efficiency., Comment: 104 pages, 28 figures. Manuscript accepted for publication in Applied Physics Reviews

In this work, we present two types of microfluidic chips involving magnetic nanoparticles dispersed in cyclohexane with oleic acid. In the first case, the hydrophobically coated nanoparticles are self-assembled with an amphiphilic diblock copolymer by a double-emulsion process in order to prepare giant magnetic vesicles (polymersomes) in one step and at a high throughput. It was shown in literature that such diblock copolymer W/O/W emulsion droplets can evolve into polymersomes made of a thin (nanometric) magnetic membrane through a dewetting transition of the oil phase from the aqueous internal cores usually leading to "acorn-like" structures (polymer excess) sticking to the membranes. To address this issue and greatly speed up the process, the solvent removal by evaporation was replaced by a "shearing-off" of the vesicles in a simple PDMS chip designed to exert a balance between a magnetic gradient and viscous shear. In the second example, a simple oil-in-oil emulsion chip is used to obtain regular trains of magnetic droplets that circulate inside an inductor coil producing a radio-frequency magnetic field. We evidence that the heat produced by magnetic hyperthermia can be converted into a temperature rise even at the scale of nL droplets. The results are compared to heat transfer models in two limiting cases: adiabatic vs. dissipative. The aim is to decipher the delicate puzzle about the minimum size required for a tumor "phantom" to be heated by radio-frequency hyperthermia in a general scope of anticancer therapy., Comment: The 9th International Conference on the Scientific and Clinical Applications of Magnetic Carriers May 22-26, 2012, Minneapolis, MN, USA Session 1: Nanotechnology, IEEE Transactions on Magnetism 2012

Hydrophobically modified magnetic nanoparticles (MNPs) were encapsulated within the membrane of poly(trimethylene carbonate)-b-poly(L-glutamic acid) (PTMC-b-PGA) block copolymer vesicles using a nanoprecipitation process. This formulation method provides a high loading of MNPs (up to 70 wt %) together with a good control over the sizes of the vesicles (100 - 400 nm). The deformation of the vesicle membrane under an applied magnetic field was evidenced by anisotropic SANS. These hybrid objects display contrast enhancement properties in Magnetic Resonance Imaging, a diagnostic method routinely used for three-dimensional and non-invasive scans of the human body. They can also be guided in a magnetic field gradient. The feasibility of drug release triggered by magnetic induction was evidenced using the anticancer drug doxorubicin (DOX), which is co-encapsulated in the membrane. Magnetic polymersomes are thus proposed as multimodal drug nanocarriers for bio-imaging and magneto-chemotherapy.

The elaboration of multimodal nanoparticles stimulates tremendous interest owing to their numerous potentialities in many applicative fields like optoelectronics, photonics and especially bioimaging. The concomitant association of various properties (optical, electrochemical, magnetic) allows for the use of complementary stimuli in order to probe the interactions between the nanoparticles and their surroundings.Nanoparticles (NPs) have thus become highly praised tools to image cells and tissues with a large contrast compatible with the dimensions of biological materials and the existence of quantum confinement effects induced by the reduced dimensions. In this context, the combination of magnetism and emissive properties such as fluorescence appears particularly attractive for non-invasive investigations, cell sorting or drug vectorization. Therefore, combining both fluorescence and magnetism requires the delicate construction of hybrid assemblies. Most of the magnetic nanoparticles are made of metallic oxides or alloys, e.g. gamma-Fe2O3, Fe3O4, FePt, while the target fluorescent entities are often organic dyes or quantum dots (QDs)., Comment: 9 figures, 1 table, 7 pages - to appear in Small 2009

A novel type of hybrid colloids is presented, based on the association of several polymeric systems and ferrofluids. On the one hand, we use inorganic nanoparticles made of magnetic iron oxide prepared at the LI2C, which response to a magnetic field of low intensity. On the other hand the organic part is made either of long linear polyacrylamide chains or of mesoscopic structures (vesicles and micelles) self-assembled from amphiphile polybutadiene-b-poly(glutamic acid) di-block copolymers, which conformation is pH-sensitive.

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-Fe2O3) and cationic-neutral copolymers. The copolymers investigated are poly(trimethylammonium ethylacrylate methylsulfate)-b-poly(acrylamide), with molecular weights 5000-b-30000 gmol-1 and 110000-b-30000 gmol-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) between several tens to several 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., Comment: 7 figures, 7 pages, 52 references