Physical and Chemical Properties of Magnetite and Magnetite-Polymer Nanoparticles and Their Colloidal Dispersions

The properties of polymer-coated magnetite nanoparticles, which have the potential to be used as effective magnetic resonance contrast agents, have been studied. The magnetite particles were synthesized by using continuous synthesis in an aqueous solution. The polymer-coated magnetite nanoparticles were synthesized by seed precipitation polymerization of methacrylic acid and hydroxyethyl methacrylate in the presence of the magnetite nanoparticles. The particle size was measured by laser light scattering. It was shown that the particle size, variance, magnetic properties, and stability of aqueous magnetite colloidal dispersion strictly depend on the nature of the stabilizing agent. The average hydrodynamic radius of the magnetite particles was found to be 5.7 nm in the stable aqueous colloidal dispersion. An inclusion of the magnetite particle into a hydrophilic polymeric shell increases the stability of the dispersion and decreases the influence of the stabilizing agent on the magnetic and structural properties of the magnetite particles as was shown by X-ray diffraction and M?ssbauer and IR spectroscopy, as well as by vibrating sample magnetometry. The variation in the polymeric shell size and the polymer net density can be useful tools for evaluation of the polymer-coated magnetite particles as effective contrast agents. Copyright 1999 Academic Press.     

Structure of polymer-stabilized magnetic fluids: small-angle neutron scattering and mean-field lattice modeling

Small-angle neutron scattering and mean-field lattice modeling were used to characterize a class of water-based magnetic fluids tailored specifically to extract soluble organic compounds from water. The fluids consist of a suspension of approximately 7 nm magnetite (Fe3O4) nanoparticles coated with a bifunctional polymer layer comprised of an outer hydrophilic poly(ethylene oxide) (PEO) region for colloidal stability and an inner hydrophobic poly(propylene oxide) (PPO) region for solubilization of organic compounds. The inner region of the polymer shell is increasingly depleted of water as the fraction of PPO side chains increases. The incorporation of PPO side chains also leads to a small increase in interparticle attraction. The lattice model predicted a shell structure similar to that of a PEO-PPO-PEO triblock copolymer (Pluronic) micelle, with equivalent levels of hydration but with more PEO present in the PPO-rich regions, as the side chains grafted to the surface are less able to segregate than when in free micellar systems.     

Synthesis and surface treatment of magnetite nanoparticles for tuning hydrophobicity and colloidal stability

Post-synthetic surface modification of magnetite nanoparticles synthesized by a modified co-precipitation process was carried out with triethoxy-terminated perfluoropolyether (PFPE) oligomers. The chemisorption of PFPE oligomers on the surface of magnetites was confirmed by ATR-FTIR and TGA analyses. The efficiency of surface modification of the oligomer to prevent the aggregation of magnetite nanoparticles was studied with the dynamic light scattering technique by measuring the hydrodynamic diameter and polydispersity index of the surface treated nanoparticles, together with their zeta potential. Aggregation kinetics profiles were constructed for surface treated nanoparticles. The obtained data was compared with magnetite nanoparticles treated with critic acid, to assess the efficiency of the surface modification with the PFPE oligomers. The comparison showed that the bifunctional PFPE oligomer treated nanoparticles are characterized by improved colloidal stability and hydrophobicity.     

Facile synthesis of superparamagnetic magnetite nanoparticles in liquid polyols

Magnetite nanoparticles have been successfully synthesized in liquid polyols at elevated temperature. Polyol solvent plays a crucial role in determining the morphology and colloidal stability of the resulting particles. The structure and morphology of the nanoparticles were studied using XRD, TEM, SAED, TGA and FTIR. The magnetic properties of the samples were measured using physical properties measurement system (PPMS) of Quantum Design. The results show that as-prepared magnetite nanoparticles are monodisperse, highly crystalline and superparamagnetic at room temperature. The nanoparticles can be easily dispersed in aqueous media and other polar solvents due to coated by a layer of hydrophilic polyol ligands in situ. This approach provides a facile route to prepare magnetite nanoparticles.     

Double hydrophilic block copolymer monolayer protected hybrid gold nanoparticles and their shell cross-linking

This paper describes the syntheses of core/shell gold nanoparticles stabilized with a monolayer of double hydrophilic block copolymer and their stimuli responsiveness before and after shell cross-linking. The hybrid nanoparticles consist of gold core, cross-linkable poly(2-(dimethylamino)ethyl methacrylate) (PDMA) inner shell, and poly(ethylene oxide) (PEO) corona. First, diblock copolymer PEO-b-PDMA was prepared via the reversible addition-fragmentation chain transfer (RAFT) technique using a PEO-based macroRAFT agent. The dithioester end group of PEO-b-PDMA diblock copolymer was reduced to a thiol end group. The obtained PEO-b-PDMA-SH was then used to prepare diblock copolymer stabilized gold nanoparticles by the "grafting-to" approach. 1,2-Bis(2-iodoethoxy)ethane (BIEE) was utilized to selectively cross-link the PDMA residues in the inner shell. The stimuli responsiveness and colloidal stability of core/shell gold nanoparticles before and after shell cross-linking were characterized by laser light scattering (LLS), UV-vis transmittance, and transmission electron microscopy (TEM). At pH 9, the average hydrodynamic radius Rh of non-cross-linked hybrid gold nanoparticles starts to increase above 35 degrees C due to the lower critical solution temperature (LCST) phase behavior of the PDMA blocks in the inner shell. In contrast, Rh of the shell cross-linked gold nanoparticles were essentially independent of temperature. Core/shell gold nanoparticles before and after shell cross-linking exhibit reversible swelling on varying the solution pH. Compared to non-cross-linked core/shell gold nanoparticles, shell cross-linking of the hybrid gold nanoparticles leads to permanent core/shell nanostructures with much higher colloidal stability and physically isolates the gold core from the external environment.     

Photocatalytic and magnetic titanium dioxide/polystyrene/magnetite composite hybrid polymer particles

Novel multifunctional titanium dioxide (TiO₂)/polystyrene/magnetite composite hybrid polymer particle dispersions with TiO₂ nanoparticles in the surface and magnetite nanoparticles encapsulated inside the polymer matrix were produced by Pickering miniemulsion polymerization in one single step. Whereas TiO₂ nanoparticles were used to impart photocatalytic functionality and colloidal stability, magnetite nanoparticles were incorporated to allow an easy extraction for recovery and reuse of the composite multifunctional particles. The morphology of the composite particles was assessed by scanning transition electron microscopy (STEM) and energy‐dispersive X‐ray spectroscopy (EDX). The paramagnetism of the particles was analyzed using a SQUID magnetometer and their photocatalytic activity was assessed by degrading methylene blue (MB) solutions under UV light and by recovering and reusing of the particles in five consecutive cycles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3350–3356     

Star-block copolymers as templates for the preparation of stable gold nanoparticles

Gold nanoparticles of improved stability against aggregation were prepared using poly(ethylene oxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) star-block copolymers. A five-arm star-shaped macroinitiator (PEO) was utilized for the automated parallel controlled ring-opening polymerization of epsilon-caprolactone to prepare a series of PEO-b-PCL star-block copolymers with a constant PEO core linked to PCL blocks of variable length. The PEO core was swelled with KAuCl4 in N,N-dimethylformamide (DMF), and gold nanoparticles were subsequently obtained by reduction with NaBH4. Since the process was always templated by the same PEO core for all investigated polymers, the average dimension of the formed gold nanoparticles was in the same range for all star-block copolymers. In sharp contrast, the size distribution and long-term stability against aggregation of the gold nanoparticles dispersed in DMF were strongly dependent on the PCL block length, confirming the role of PCL blocks as stabilizing blocks for these nanoparticles.     

Loading magnetic nanoparticles into sperm cells does not affect their functionality

The spontaneous loading of magnetite nanoparticles into sperm cell was carried out by mixing an aqueous colloidal solution of Fe3O4-PVA with sperm cells (10(8) cells/ml) for 2 h at 37 degrees C suspended in glucose-free modified Tyrode solution. The penetration of the magnetite nanoparticles into the sperm cells was monitored by conventional analytical chemistry. We have demonstrated that the motility and the ability to undergo the acrosome reaction (i.e., the ability to fertilize the egg) were not affected by the presence of the magnetite nanoparticles.     

Hamaker constants of iron oxide nanoparticles

The Hamaker constants for iron oxide nanoparticles in various media have been calculated using Lifshitz theory. Expressions for the dielectric responses of three iron oxide phases (magnetite, maghemite, and hematite) were derived from recently published optical data. The nonretarded Hamaker constants for the iron oxide nanoparticles interacting across water, A(1w1) = 33 - 39 zJ, correlate relatively well with previous reports, whereas the calculated values in nonpolar solvents (hexane and toluene), A(131) = 9 - 29 zJ, are much lower than the previous estimates, particularly for magnetite. The magnitude of van der Waals interactions varies significantly between the studied phases (magnetite < maghemite < hematite), which highlights the importance of a thorough characterization of the particles. The contribution of magnetic dispersion interactions for particle sizes in the superparamagnetic regime was found to be negligible. Previous conjectures related to colloidal stability and self-assembly have been revisited on the basis of the new Lifshitz values of the Hamaker constants.     

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.     

Association between branched poly(ethyleneimine) and sodium dodecyl sulfate in the presence of neutral polymers

In the present paper, the effect of different neutral polymers on the self-assemblies of hyperbranched poly(ethyleneimine) (PEI) and sodium dodecyl sulfate (SDS) has been investigated at different ionization degrees of the polyelectrolyte molecules. The investigated uncharged polymers were poly(ethyleneoxide), poly(vinylpyrrolidone) and dextran samples of different molecular mass. Dynamic light scattering and electrophoretic mobility measurements demonstrate that the high molecular mass PEO or PVP molecules adsorb considerably onto the surface of the PEI/SDS nanoparticles. At appropriate concentrations of PVP or PEO, sterically stabilized colloidal dispersions of the polyelectrolyte/surfactant nanoparticles with hydrophobic core and hydrophilic corona can be prepared. These dispersions have considerable kinetic stability at high ionic strengths where the accelerated coagulation of the PEI/SDS nanoparticles results in precipitation in the absence of the neutral polymers. In contrast, the addition of dextran does not affect considerably the kinetic stability of PEI/SDS mixtures because of its low adsorption affinity towards the surface of the polyelectrolyte/surfactant nanoparticles.     

Control of the PEO chain conformation on nanoparticles by adsorption of PEO-block-poly(L-lysine) copolymers and its significance on colloidal stability and protein repellency

The physical adsorption of PEO(n)-b-PLL(m) copolymers onto silica nanoparticles and the related properties of poly(ethylene oxide) (PEO)-coated particles were studied as a function of the block copolymer composition. Copolymers adopt an anchor-buoy conformation at the particle surface owing to a preferential affinity of poly(L-lysine) (PLL) blocks with the silica surface over PEO blocks when a large excess of copolymer is used. The interdistance between PEO chains at particle surface is highly dependent on the size of PLL segments; a dense brush of PEO is obtained for short PLL blocks (DP = 10), whereas PEO chains adopt a so-called interacting "mushroom" conformation for large PLL blocks (DP = 270). The size of the PEO blocks does not really influence the copolymer surface density, but it has a strong effect on the PEO layer thickness as expected. Salt and protein stability studies led to similar conclusions about the effectiveness of a PEO layer with a dense brush conformation to prevent colloidal aggregation and protein adsorption. Besides, a minimal PEO length is required to get full stabilization properties; as a matter of fact, both PEO(45)-b-PLL(10) and PEO(113)-b-PLL(10) give rise to a PEO brush conformation but only the latter copolymer efficiently stabilizes the particles in the presence of salt or proteins.     

Nonpolymeric Coatings of Iron Oxide Colloids for Biological Use as Magnetic Resonance Imaging Contrast Agents

Iron oxide nanoparticles are used in vivo as contrast agents in magnetic resonance imaging. Their widely used polymer coatings are directly involved in their biocompatibility and avoid magnetic aggregation. As these polymer brushes also limit their tissular diffusion due to important hydrodynamic sizes, this work looks to obtain particles coated with thin layers of organic biocompatible molecules. Coating molecules were chosen depending on their fixation site on iron cores; carboxylates, sulfonates, phosphates, and phosphonates, and, among them, analogs of the phosphorylcholine. Two coating procedures (dialysis and exchange resins purification) were evaluated for hydrodynamic size, total iron concentration, electrophoretic mobility, and colloidal stability. Furthermore, a complementary test on stainless steel plates evaluated the contamination by competition of phosphonates as a rough estimation of the biocompatibility of the particles. Coating with bisphosphonates, the more interesting fixation moiety, leads to small (less than 15 nm) and stable objects in a wide range of pH including the neutrality. From stability data, the coating density was evaluated at around 1.6 molecules per nm(2). Including a quaternary ammonium salt to the coating molecule lowers their electrophoretic mobility. Moreover, this type of coating protects steel plates against contamination without significant desorption. All these properties allow further developments of these nanoparticles for biomedical applications. Copyright 2001 Academic Press.     

Enhancing Tumor Cell Response to Chemotherapy through the Targeted Delivery of Platinum Drugs Mediated by Highly Stable,Multifunctional Carboxymethylcellulose‐Coated Magnetic Nanoparticles

The fabrication of nanoparticles using different formulations, and which can be used for the delivery of chemotherapeutics, has recently attracted considerable attention. We describe herein an innovative approach that may ultimately allow for the selective delivery of anticancer drugs to tumor cells by using an external magnet. A conventional antitumor drug, cisplatin, has been incorporated into new carboxymethylcellulose‐stabilized magnetite nanoparticles conjugated with the fluorescent marker Alexa Fluor 488 or folic acid as targeting agent. The magnetic nanocarriers possess exceptionally high biocompatibility and colloidal stability. These cisplatin‐loaded nanoparticles overcome the resistance mechanisms typical of free cisplatin. Moreover, experiments aimed at the localization of the nanoparticles driven by an external magnet in a medium that mimics physiological conditions confirmed that this localization can inhibit tumor cell growth site‐specifically.     

Controlled clustering and enhanced stability of polymer-coated magnetic nanoparticles

The clustering and stability of magnetic nanoparticles coated with random copolymers of acrylic acid, styrenesulfonic acid, and vinylsulfonic acid has been studied. Clusters larger than 50 nm are formed when the coatings are made using too low or too high molecular weight polymers or using insufficient amounts of polymer. Low-molecular-weight polymers result in thin coatings that do not sufficiently screen van der Waals attractive forces, while high-molecular-weight polymers bridge between particles, and insufficient polymer results in bare patches on the magnetite surface. The stability of the resulting clusters is poor, but when an insufficient polymer is used as primary coating, and a secondary polymer is added to coat remaining bare magnetite, the clusters are stable in high salt concentrations (>5 M NaCl), while retaining the necessary cluster size for efficient magnetic recovery. The magnetite cores were characterized by TEM and vibrating sample magnetometry, while the clusters were characterized by dynamic light scattering. The clustering and stability are interpreted in terms of the particle-particle interaction forces, and the optimal polymer size can be predicted well on the basis of these forces and the solution structure and hydrophobicity of the polymer. The size of aggregates formed by limited polymer can be predicted with a diffusion-limited colloidal aggregation model modified with a sticking probability based on fractional coating of the magnetite cores.     

Magnetite nanorod thermotropic liquid crystal colloids: Synthesis, optics and theory

We have developed a facile method for preparing magnetic nanoparticles which couple strongly with a liquid crystal (LC) matrix, with the aim of preparing ferronematic liquid crystal colloids for use in magneto-optical devices. Magnetite nanoparticles were prepared by oxidising colloidal Fe(OH)(2) with air in aqueous media, and were then subject to alkaline hydrothermal treatment with 10moldm(-3) NaOH at 100°C, transforming them into a polydisperse set of domain magnetite nanorods with maximal length ～500nm and typical diameter ～20nm. The nanorods were coated with 4-n-octyloxybiphenyl-4-carboxylic acid (OBPh) and suspended in nematic liquid crystal E7. As compared to the conventional oleic acid coating, this coating stabilizes LC-magnetic nanorod suspensions. The suspension acts as a ferronematic system, using the colloidal particles as intermediaries to amplify magnetic field-LC director interactions. The effective Frederiks magnetic threshold field of the magnetite nanorod-liquid crystal composite is reduced by 20% as compared to the undoped liquid crystal. In contrast with some previous work in this field, the magneto-optical effects are reproducible on time scales of months. Prospects for magnetically switched liquid crystal devices using these materials are good, but a method is required to synthesize single magnetic domain nanorods.     

Poly(ethylene oxide) macromonomer-grafted polymer nanoparticles synthesised by emulsifier-free emulsion polymerisation

Ultrafine polymer nanoparticles based on poly(ethylene oxide) (PEO) macromonomer-grafted polystyrene (PS) have been synthesised by emulsifier-free emulsion polymerisation. In addition to the binary copolymerisation between PEO macromonomer and styrene, ternary copolymerisations were also conducted in the presence of a cationic monomer (2-(methacryloyloxy)ethyl) trimethylammonium chloride (MATMAC) as a second comonomer. The size and charge characteristics of fine nanoparticles were characterised using both photon correlation spectroscopy and transmission electron microscopy techniques as well as colloidal titration. It was found that after PEO chains (repeat unit 9 or higher) were incorporated into the PS latex, the particle size was significantly reduced owing to the steric effect contributed from grafted PEO chains. Ternary copolymerisation using MATMAC as comonomer further reduced the particle size, leading to nanoparticles as small as 60 nm. Increasing the MATMAC feed ratio gradually reduced the final size of the nanoparticle, owing to the enhancement in electrostatic stabilisation, whereas increasing the PEO macromonomer feed ratios led to slightly larger particles but significantly inhibited the agglomeration of primary particles. The formation mechanism of the nano- or microparticles with various sizes during polymerisation is discussed in terms of nucleation, agglomeration and adsorption of primary particles.     

Reversible controlled assembly of thermosensitive polymer-coated gold nanoparticles

Aggregation of thermosensitive polymer-coated gold nanoparticles was performed in aqueous solution in the presence of a triblock copolymer poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic P123, PEO(20)-PPO(68)-PEO(20)). The gold nanoparticles, AuNPs, which are covered by thermosensitive statistical copolymers poly(EO(x)-st-PO(y)), aggregate when the temperature is higher than the phase transition temperature of the polymer, leading to a macroscopic precipitation. The presence of Pluronic chains in solution prevents the uncontrolled aggregation of the AuNPs at higher temperature than both the aggregation temperature of the AuNPs (T(agg)) and the critical micellization temperature (cmt) of the Pluronic. The size, the colloidal stability, and the optical properties of the AuNPs aggregates are modulated as a function of the P123-to-AuNP ratio, which constitutes the critical parameter of the system. Moreover, the AuNP aggregation is totally reversible upon decreasing the temperature below T(agg). Our approach constitutes an easy way to the formation of well-controlled nanoparticle aggregates with well-defined sizes. The resulting aggregates have been characterized by UV-vis spectroscopy, dynamic light scattering, and electron microscopy.     

Stability of mixtures of charged silica, silica-alumina, and magnetite colloids

We report experiments on the stability of aqueous mixtures of charged colloidal magnetite and charged silica and silica covered with alumina particles of similar size. First, positively charged magnetite dispersions were mixed with negatively charged silica dispersions at pH 4, at different volume ratios and low colloid volume fractions, producing mixtures which were stable over a period of weeks despite the expected electrostatic attraction between the oppositely charged particles. When magnetite particles were mixed with positively charged silica covered with alumina at pH 4 under exactly the same conditions, some of the systems separated to form a magnetite sediment. When the volume fraction of the initial dispersions was increased, the behavior of the mixtures was the opposite: positive magnetite/negative silica mixtures were unstable at intermediate volume ratios. The unexpected behavior of the mixtures was investigated by means of electrophoretic mobility, initial susceptibility, and dynamic light scattering measurements as well as sedimentation experiments.     

Adsorption of polyethylene oxide on surface modified silica – stability of bare and covered particles in suspension

 The adsorption of poly-ethylene oxide (PEO) on modified colloidal silica and the stability of the aqueous suspension was investigated. With octanol some silanol groups at the silica surface were replaced by octylgroups. The size of the modified silica particles and the charge and chemical groups on the surface were charaterized by ultracentrifugation, photon correlation spectrometry, polyelectrolyte titration and IR spectrometry. The adsorbed amounts of polyethylene oxides of different molar mass were determined on the modified silica in water. With photon correlation spectrometry (PCS) the hydrodynamic layer thickness of the PEO layers on the particles were measured. The dependences of the layer thicknesses on molar mass of the PEO, polymer concentration and adsorption time were determined. The aggregation of the suspended PEO coated and uncoated modified silica particles was examined with PCS by the time dependence of the diffusion coefficient at different salt concentrations. The influence of molar mass and concentration of PEO as well as of the age of the dispersion was explored. The measured dependences are discussed and compared with the behavior of unmodified silica- and latex-particles. Received: 6 April 1998 Accepted: 27 May 1998