Size-sorted anionic iron oxide nanomagnets as colloidal mediators for magnetic hyperthermia

Iron oxide colloidal nanomagnets generate heat when subjected to an alternating magnetic field. Their heating power, governed by the mechanisms of magnetic energy dissipation for single-domain particles (Brown and Néel relaxations), is highly sensitive to the crystal size, the material, and the solvent properties. This study was designed to distinguish between the contributions of Néel and Brownian mechanisms to heat generation. Anionic nanocrystals of maghemite and cobalt ferrite, differing by their magnetic anisotropy, were chemically synthesized and dispersed in an aqueous suspension by electrostatic stabilization. The particles were size-sorted by successive electrostatic phase separation steps. Parameters governing the efficiency of nanomagnets as heat mediators were varied independently; these comprised the particle size (from 5 to 16.5 nm), the solvent viscosity, magnetic anisotropy, and the magnetic field frequency and amplitude. The measured specific loss powers (SLPs) were in quantitative agreement with the results of a predictive model taking into account both Néel and Brown loss processes and the whole particle size distribution. By varying the carrier fluid viscosity, we found that Brownian friction within the carrier fluid was the main contributor to the heating power of cobalt ferrite particles. In contrast, Néel internal rotation of the magnetic moment accounted for most of the loss power of maghemite particles. Specific loss powers were varied by 3 orders of magnitude with increasing maghemite crystal size (from 4 to 1650 W/g at 700 kHz and 24.8 kA/m). This comprehensive parametric study provides the groundwork for the use of anionic colloidal nanocrystals to generate magnetically induced hyperthermia in various media, including complex systems and biological materials.     

Highly magnetic latexes from submicrometer oil in water ferrofluid emulsions

The synthesis of functionalized submicrometer magnetic latex particles is described as obtained from a preformed magnetic emulsion composed of organic ferrofluid droplets dispersed in water. Composite (polystyrene/γ‐Fe₂O₃) particles were prepared according to a two‐step procedure including the swelling of ferrofluid droplets with styrene and a crosslinking agent (divinyl benzene) followed by seeded emulsion polymerization with either an oil‐soluble [2,2′‐azobis(2‐isobutyronitrile)] or water‐soluble (potassium persulfate) initiator. Depending on the polymerization conditions, various particle morphologies were obtained, ranging from asymmetric structures, for which the polymer phase was separated from the inorganic magnetic phase, to regular core–shell morphologies showing a homogeneous encapsulation of the magnetic pigment by a crosslinked polymeric shell. The magnetic latexes were extensively characterized to determine their colloidal and magnetic properties. The desired core–shell structure was efficiently achieved with a given styrene/divinyl benzene ratio, potassium persulfate as the initiator, and an amphiphilic functional copolymer as the ferrofluid droplet stabilizer. Under these conditions, ferrofluid droplets were successfully turned into superparamagnetic polystyrene latex particles, about 200 nm in size, containing a large amount of iron oxide (60 wt %) and bearing carboxylic surface charges. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2642–2656, 2006     

Studies about the influence of self-organization of colloidal magnetic nanoparticles on the magnetic Néel relaxation time

The monodomain magnetic nanoparticle-based colloids are mainly used in biomedical applications. In this type of colloids, there is a tendency of agglomeration even in the absence of external magnetic field. So, the Néel magnetic relaxation time of the system is affected by that tendency. In this paper, we propose a model to study how the nanoparticle tendency to agglomerate in the nanofluid affects the Néel relaxation time of the system. For simulating the self-organization of colloidal nanoparticles, we apply a Monte Carlo method, and the Néel magnetic relaxation time is assessed through the adaptation and solution of Coffey equations in oblique magnetic field, adapted to the local magnetic field on a nanoparticle.     

Fe1−yO Nanoparticles: Organometallic Synthesis and Magnetic Properties

Non‐stoichiometric wüstite particles (Fe_1?yO) are synthesized using the controlled room‐temperature hydrolysis of the organometallic precursor {Fe[N(SiMe₃)₂]₂}. Particles stabilized by hexadecylamine with a diameter of ～5 nm are obtained. For such small nanoparticles, a distorted crystallographic structure is evidenced by wide‐angle X‐ray scattering at room temperature and reported for the first time. The study of the magnetic properties indicates that these particles are composed of an antiferromagnetic core surrounded by a ferromagnetic shell. According to the Néel theory, we demonstrate that this shell consists of 1.5 % of Fe³⁺ ions ferromagnetically coupled with Fe²⁺ ions.     

Magnetic poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization in the presence of electrostatically stabilized ferrofluids

Fine magnetite nanoparticles, both electrostatically stabilized and nonstabilized, were synthesized in situ by precipitation of Fe(II) and Fe(III) salts in alkaline medium. Magnetic poly(glycidyl methacrylate) (PGMA) microspheres with core‐shell structure, where Fe₃O₄ is the magnetic core and PGMA is the shell, were obtained by dispersion polymerization initiated with 2,2′‐azobisisobutyronitrile (AIBN), 4,4′‐azobis(4‐cyanovaleric acid) (ACVA), or ammonium persulfate (APS) in ethanol containing poly(vinylpyrrolidone) or ethylcellulose stabilizer in the presence of iron oxide ferrofluid. The average microsphere size ranged from 100 nm to 2 μm. The effects of the nature of ferrofluid, polymerization temperature, monomer, initiator, and stabilizer concentration on the PGMA particle size and polydispersity were studied. The particles contained 2–24 wt % of iron. AIBN produced larger microspheres than APS or ACVA. Polymers encapsulating electrostatically stabilized iron oxide particles contained lower amounts of oxirane groups compared with those obtained with untreated ferrofluid. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5827–5837, 2004     

Magnetic nanoparticles for power absorption: Optimizing size, shape and magnetic properties

We present a study on the magnetic properties of naked and silica-coated Fe₃O₄ nanoparticles with sizes between 5 and 110 nm. Their efficiency as heating agents was assessed through specific power absorption (SPA) measurements as a function of particle size and shape. The results show a strong dependence of the SPA with the particle size, with a maximum around 30 nm, as expected for a Néel relaxation mechanism in single-domain particles. The SiO₂ shell thickness was found to play an important role in the SPA mechanism by hindering the heat outflow, thus decreasing the heating efficiency. It is concluded that a compromise between good heating efficiency and surface functionality for biomedical purposes can be attained by making the SiO₂ functional coating as thin as possible.     

Structural transformations in magnetic suspensions

Structural transformations in dispersions of micron-sized iron particles suspended in a magnetite ferrofluid (the colloidal suspension of ferromagnetic nanoparticles in nonmagnetic liquid) are theoretically considered. An attempt is made to explain the tendency of iron particles to form doublets and longer chain aggregates with finite distance between particles in external magnetic field observed in recent experiments; in colloidal ferrofluid, micron-sized iron particles approach one another to finite distance that is equal approximately to the particle diameter. At moderate magnetic fields, minimal distance between approached particles is nearly independent of the strength of magnetic field. In ordinary magnetorheological dispersions, which are suspensions of magnetizing micron-sized particles in nonmagnetic liquid, the approach of particles practically does not occur up to their physical contact.     

Molecular selective photocatalysis by TiO2/nanoporous silica core/shell particulates

The coating of TiO(2) particles (P25) by a nanoporous silica layer was conducted to impart molecular recognitive photocatalytic ability. TiO(2)/nanoporous silica core/shell particles with varied pore diameters of the shell were synthesized by the reaction of P25 with an aqueous mixture of tetraethoxysilane and alkyltrimethylammonium chloride with varied alkyl chain lengths, followed by calcination. The TEM and nitrogen adsorption/desorption isotherms of the products showed that a nanoporous silica shell with a thickness of ca. 2nm and controlled pore diameter (1.2, 1.6, and 2.7 nm) was deposited on the titania particle when surfactants with different alkyl chain lengths (C12, C16 and C22) were used. The water vapor adsorption/desorption isotherms of the core/shell particles revealed that a larger amount of water adsorbed on the core/shell particles when the pore diameter is larger. The (29)Si MAS NMR spectra of the core/shell particles showed that the amount of surface silanol groups was independent of the water vapor adsorption capacity of the products. The possible molecular recognitive photocatalysis on the products was investigated under UV irradiation using two kinds of aqueous mixtures containing different organic compounds with varied sizes and functional groups: a 4-butylphenol, 4-hexylphenol, and 4-nonylphenol mixture and a 2-nitrophenol, 2-nitro-4-phenylphenol, and 4-nitro-2,6-diphenylphenol mixture. It was found that the core/shell particles exhibited selective adsorption-driven molecular recognitive photocatalytic decomposition of 4-nonylphenol and 2-nitrophenol in the two mixtures.     

Elaboration of monodisperse spherical hollow particles with ordered mesoporous silica shells via dual latex/surfactant templating: radial orientation of mesopore channels

Monodisperse spherical hollow nanoparticles of mesoporous silica featuring mesopores with a radial orientation in the silica shell were synthesized via a dual-templating method. Specifically designed polystyrene latexes with anionic or cationic surface charges acted as the core templates, while cetyltrimethylammonium bromide served as a co-template to structure the mesopore formation during tetraethoxysilane hydrolysis/condensation. The particles were well-separated and presented homogeneous mesoporous silica shells. Average particle diameters were less than 200 nm, and the particles displayed high values of specific surface area and pore volume. The shell thickness and the hollow core diameter could be tuned independently while the radial pore structure was preserved. A detailed analysis of the nitrogen adsorption-desorption isotherms proved that the central cavity was completely isolated from the external medium, that is, only accessible through the radial mesopores of the shell. Consequently, our particles gather the advantages of a well-defined structure, straight penetrating channels across the silica shell, and a high accessible porous volume of the central core. These properties make them far better candidates than simple mesoporous particles for any storage and/or controlled release applications.     

Magnetic field induced anomalous Core-Shell magnetic behavior in short-rod Co3O4

It is found that both spinel structure inversion and the Néel temperature of short-rod Co₃O₄ are dependent on the applied magnetic field. Spinel structure inversion induced by the applied field results in the change of uncompensated surface spins. Thus, the shell magnetic behavior of short-rod Co₃O₄ is also field-dependent, which shows ferrimagnetism (FIM) under the low field and antiferromagnetism (AFM) in a high field. This changing shell magnetic behavior leads to anomalous Core-Shell magnetic behavior, that Néel temperature (∼28 K) disappears under the low field and appears again in a high field.     

Synthesis of polymer-stabilized magnetic nanoparticles and fabrication of nanocomposite fibers thereof using electrospinning

Polymer-stabilized magnetic nanoparticles were obtained using two biocompatible polyelectrolytes: N-carboxyethylchitosan (CECh) and poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS). The size of the particles (mean diameter 10 or 30 nm, respectively) and the stability of the dispersions could be effectively controlled depending on the polyelectrolyte nature. The presence of polyelectrolyte shell was proved by transmission electron microscopy (TEM) studies and confirmed by thermogravimetric analyses. Depending on the polyelectrolyte nature the magnetic nanoparticles existed in different magnetic states - superparamagnetic or intermediate state between superparamagnetic and ferrimagnetic one, as evidenced by the measurements of the magnetization and Mössbauer analyses. Fabrication of nanocomposite magnetic fibers with mean diameter in the range 100-500 nm was achieved using electrospinning of the system CECh/ferrofluid/non-ionogenic polymer.     

Self-stabilized magnetic polymeric composite nanoparticles by emulsifier-free miniemulsion polymerization

Self-stabilized magnetic polymeric composite nanoparticles (SS-MPCPs) were prepared by emulsifier-free miniemulsion polymerization using styrene (St) as a monomer, sodium p-styrenesulfonate (NaSS) as an ionic comonomer, hexadecane (HD) as a hydrophobe, and 2,2'-azodiisobutyronitrile (AIBN) as an initiator in the presence of hydrophobic magnetite particles. The hydrophobic magnetite particles with an average size of about 10 nm were prepared by the acidification of the water-based magnetite ferrofluid, previously synthesized by a chemical coprecipitation method. Some colloidal features of the synthesized SS-MPCPs were analyzed. The morphology and the particle size distributions (PSDs) of the SS-MPCPs were observed and analyzed by transmission electron microscopy (TEM). The surface charge density was determined by conductometric titration. The surface hairy layer and the colloidal stability of SS-MPCPs against different electrolytes were determined by photon correlation spectroscopy (PCS). The average Fe3O4 content of SS-MPCPs was determined by thermogravimetric analysis (TGA). Vibrating sample magnetometry (VSM) was used to analyze the magnetic properties of the SS-MPCPs under dry conditions. The results show that the encapsulation of magnetite is successful and the distribution of magnetite particles inside SS-MPCPs is mainly in the core of the particles. The best SS-MPCPs prepared had a relatively narrow PSD, exhibited superparamagnetism, and possessed some magnetic response.     

Fabrication and characterization of mesoporous Co3O4 core/mesoporous silica shell nanocomposites

A mesoporous Co(3)O(4) core/mesoporous silica shell composite with a variable shell thickness of 10-35 nm was fabricated by depositing silica on Co(3)O(4) superlatticed particles. The Brunauer-Emmett-Teller (BET) surface area of the composite with a shell thickness of ca. 2.0 nm was 238.6 m(2)/g, which varied with the shell thickness, and the most frequent pore size of the shell was ca. 2.0 nm. After the shell was eroded with hydrofluoric acid, mesoporous Co(3)O(4) particles with a pore size of ca. 8.7 nm could be obtained, whose BET surface area was 86.4 m(2)/g. It is proposed that in the formation of the composite the electropositive cetyltrimethylammonium bromide (CTAB) micelles were first adsorbed on the electronegative Co(3)O(4) particle surface, which directed the formation of the mesoporous silica on the Co(3)O(4) particle surface. Electrochemical measurements showed that the core/shell composites exhibited a higher discharge capacity compared with that of the bare Co(3)O(4) particles.     

State of dispersion of magnetic nanoparticles in an aqueous medium: experiments and Monte Carlo simulation

Monte Carlo simulation results predicting the state of dispersion (single, dimer, trimer, and so on) of coated superparamagnetic iron oxide (Fe(3)O(4)) nanoparticles in an aqueous medium are compared with our experimental data for the same. Measured values of the volume percentage of particles in the dispersion, core particle diameter, coating-shell thickness, grafting density of the coating agent, saturation magnetization, and zeta potential for the citric acid-coated and poly(acrylic acid) [PAA]-coated particles have been used in our simulation. The simulation was performed by calculating the total interaction potential between two nanoparticles as a function of their interparticle distance and applying a criterion for the two particles to aggregate, with the criterion being that the minimum depth of the secondary minima in the total interaction potential must be at least equal to k(B)T. Simulation results successfully predicted both experimental trends-aggregates for citric acid-coated particles and an individual isolated state for PAA-coated particles. We have also investigated how this state changes for both kind of coating agents by varying the particle volume percentage from 0.01 to 25%, the particle diameter from 2 to 19 nm, the shell thickness from 1 to 14 nm, and grafting density from 10(15) to 10(22) molecules/m(2). We find that the use of a lower shell thickness and a higher particle volume percentage leads to the formation of larger aggregates. The possible range of values of these four variables, which can be used experimentally to prepare a stable aqueous dispersion of isolated particles, is recommended on the basis of predictions from our simulation.     

Rates of ionic reactions with charged nanoparticles in aqueous media

A theory is developed to evaluate the electrostatic correction for the rate of reaction between a small ion and a charged ligand nanoparticle. The particle is assumed to generally consist of an impermeable core and a shell permeable to water and ions. A derivation is proposed for the ion diffusion flux that includes the impact of the equilibrium electrostatic field distribution within and around the shell of the particle. The contribution of the extra- and intraparticulate field is rationalized in terms of a conductive diffusion factor, f(el), that includes the details of the particle geometry (core size and shell thickness), the volume charge density in the shell, and the parameters defining the electrostatic state of the particle core surface. The numerical evaluation of f(el), based on the nonlinear Poisson-Boltzmann equation, is successfully complemented with semianalytical expressions valid under the Debye-Hückel condition in the limits of strong and weak electrostatic screening. The latter limit correctly includes the original result obtained by Debye in his 1942 seminal paper about the effect of electrostatics on the rate of collision between two ions. The significant acceleration and/or retardation possibly experienced by a metal ion diffusing across a soft reactive particle/solution interphase is highlighted by exploring the dependence of f(el) on electrolyte concentration, particle size, particle charge, and particle type (i.e., hard, core/shell, and entirely porous particles).     

Physicochemical characterisation of different welding aerosols

Physicochemical properties important in exposure characterisation of four different welding aerosols were investigated. Particle number size distributions were determined by scanning mobility particle sizer (SMPS), mass size distributions by separation and weighing the individual size fractions of an 11-stage cascade impactor. The size distribution of the primary particles of agglomerates, chemical composition and morphology of the particles were examined by TEM. There were significant differences in the particle number size distributions of the different welding aerosols according to the SMPS determinations. The particle mass size distributions determined gravimetrically were, however, not really different. The dominant range with respect to mass was between 0.1 and 1 μm, regardless of the welding technique. Most of the primary particles in all different welding aerosols had diameters between 5 and 40 nm. All types of primary particles had a tendency to form chainlike agglomerates. A clear size dependence of the particle chemical composition was encountered in the case of manual metal arc welding aerosol. Small particles with diameters below 50 nm were mostly metal oxides in contrast to larger particles which also contained more volatile elements (e.g. potassium, fluorine, sodium, sulphur).     

Synthesis and magnetic properties of silica-coated FePt nanocrystals

Colloidal FePt nanocrystals, 6 nm in diameter, were synthesized and then coated with silica (SiO2) shells. The silica shell thickness could be varied from 10 to 25 nm. As-made FePt@SiO2 nanocrystals have low magnetocrystalline anisotropy due to a compositionally disordered FePt core. When films of FePt@SiO2 particles are annealed under hydrogen at 650 degrees C or above, the FePt core transforms to the compositionally ordered L1(0) phase, and superparamagnetic blocking temperatures exceeding room temperature are obtained. The SiO2 shell prevents FePt coalescence at annealing temperatures up to approximately 850 degrees C. Annealing under air or nitrogen does not induce the FePt phase transition. The silica shell limits magnetic dipole coupling between the FePt nanocrystals; however, low temperature (5 K) and room temperature magnetization scans show slightly constricted hysteresis loops with coercivities that decrease systematically with decreased shell thickness, possibly resulting from differences in magnetic dipole coupling between particles.     

Microstructure analysis of monodisperse ferrofluid monolayers: theory and simulation

We try to elucidate the microstructure formation in a monodisperse ferrofluid monolayer. The system under study consists of soft sphere magnetic dipolar particles confined to a thin fluid layer. The positions of the particles are constrained to a 2D geometry, whereas the particle magnetic dipole moments are not fixed to the body systems, and are free to rotate in 3 dimensions, hence forming in what we call a quasi-2D geometry. Using a combination of analytical density functional theory and molecular dynamics (MD) simulations, we find that for the studied range of parameters the majority of aggregates might be divided into two types: chains and rings. Their sizes and area fractions are strongly influenced by the geometrical constraints. We show that for quasi-2D systems the excluded area effects play one of the most important parts in the microstructure formation. The simulation technique and the theoretical model put forward in the present paper agree qualitatively with the results of recent in situ observations of the microstructures observed in ferrofluid monolayers [M. Klokkenberg, R. P. A. Dullens, W. K. Regel, B. H. Erné, A. P. Philipse, Phys. Rev. Lett., 2006, 96, 037203].     

A facile synthesis of highly water-soluble, core–shell organo-silica nanoparticles with controllable size via sol–gel process

A series of highly water-soluble organo-silica nanoparticles, ranging from 2 to 10 nm in diameter, were synthesized by the cohydrolysis and copolycondensation reactions. ω-methoxy(polyethyleneoxy)propyltrimethoxysilane (PEG6-9) and hydroxymethyltriethoxysilane (HMTEOS) mixtures were catalyzed by sodium hydroxide in the presence of surfactant benzethonium chloride (BTC) with various ratios of PEG6-9/HMTEOS at room temperature. The synthesized organo-silica nanoparticles possess a core–shell structure with a core of organo-silica resulting from HMTEOS and a monolayer shell of PEG6-9. The chemo-physical characteristics of the particles were studied by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, ²⁹Si nuclear magnetic resonance (NMR), dynamic light scattering (DLS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The molecular weight and particle size of the particles increased with increasing HMTEOS molar ratios. The richest HMTEOS composition for the water-soluble particles was found to be HMTEOS:PEG6-9 = 80:20, where the particles had a 6 nm diameter core and a 0.8 nm thick shell. We propose that these water-soluble organo-silica nanoparticles will be suitable for biomedical applications.     

Poly(p‐phenylenediamine)‐coated magnetic particles: Preparation and electrochemical properties

Magnetic particles are of great interest in various biomedical applications, such as, sample preparation, in vitro biomedical diagnosis, and therapy. For biosensing applications, the used functional magnetic particles should answer numerous criteria such as; submicron size in order to avoid rapid sedimentation, high magnetic content for fast separations under applied magnetic field, and finally, good colloidal stability. Therefore, the aim of this work was to prepare submicron magnetic core and conducting polymer shell particles. The polymer shell was induced using p‐phenylenediamine as key monomer. The obtained core–shell particles were characterized in terms of particle size, size distribution, magnetization properties, Fourier transform infrared (FTIR) analysis, surface morphology, chemical composition, cyclic voltammetry, and impedance spectroscopy. The best experimental condition was found using 40 mg of povidone (PVP—stabilizing agent) and 0.16 mmol of p‐phenylenediamine. Using such initial composition, the core‐shell magnetic nanoparticles shown a narrowed size distribution around 290 nm and high magnetic content (above 50%). The obtained amino containing submicron highly magnetic particles were found to be a conducting material and superparamagnetic in nature. These promising conducting magnetic particles can be used for both transport and lab‐on‐a‐chip detection.