Magnetic activity of nanostructured biopolymeric nanomagnets

The magnetic properties of arabinogalactan-stabilized iron-containing nanobiocomposites, which include magnetite nanoparticles, were studied. The magnetic characteristics of samples were measured on a SQUID magnetometer in the temperature range of 5–320 K and magnetic fields of up to 1.5·10⁴ G. The coercive force and the residual magnetization of ferroarabinogalactan nanocomposites are inversely dependent on the magnetite nanoparticle size.     

Preparation and characterization of polypyrrole/magnetite nanocomposites synthesized by in situ chemical oxidative polymerization

This work describes the preparation and characterization of polypyrrole (PPy)/iron oxide nanocomposites fabricated from monodispersed iron oxide nanoparticles in the crystalline form of magnetite (Fe₃O₄) and PPy by in situ chemical oxidative polymerization. Two spherical nanoparticles of magnetite, such as 4 and 8 nm, served as cores were first dispersed in an aqueous solution with anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate to form micelle/magnetite spherical templates that avoid the aggregation of magnetite nanoparticles during the further preparation of nanocomposites. The PPy/magnetite nanocomposites were then synthesized on the surface of the spherical templates. Structural and morphological analysis showed that the fabricated PPy/magnetite nanocomposites are core (magnetite)‐shell (PPy) structures. Morphology of the PPy/magnetite nanocomposites containing monodispersed 4‐nm magnetite nanoparticles shows a remarkable change from spherical to tube‐like structures as the content of nanoparticles increases from 12 to 24 wt %. Conductivities of these PPy/magnetite nanocomposites show significant enhancements when compared with those of PPy without magnetite nanoparticles, in particular the conductivities of 36 wt % PPy/magnetite nanocomposites with 4‐nm magnetite nanoparticles are about six times in magnitude higher than those of PPy without magnetite nanocomposites. These results suggest that the tube‐like structures of 36 wt % PPy/magnetite nanocomposites may be served as conducting network to enhance the conductivity of nanocomposites. The magnetic properties of 24 and 36 wt % PPy/magnetitenanocomposites show ferromagnetic behavior and supermagnetism, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1291–1300, 2008     

One-pot synthesis and bioapplication of amine-functionalized magnetite nanoparticles and hollow nanospheres

To demonstrate their applications in biological and medical fields such as in immunoassays, magnetic separation of cells or proteins, drug or gene delivery, and magnetic resonance imaging, the template-free syntheses of water-soluble and surface functionalized magnetic nanomaterials have become essential and are challenging. Herein, we developed a facile one-pot template-free method for the preparation of amine-functionalized magnetite nanoparticles and hollow nanospheres by using FeCl(3)6 H(2)O as single iron source. These magnetic nanomaterials were characterized by TEM, SEM, XRD, and FTIR technologies. Their magnetic properties were also studied by using a superconducting quantum interference device (SQUID) magnetometer at room temperature. Then the amine-functionalized magnetite nanoparticles were applied to immunoassays and magnetic resonance imaging in live mice.     

Disappearance of long range spin-order in ultrafine magnetite particles

Ferromagnetic properties of ultrafine magnetite (Fe₃O₄) particles were examined by the ESR and the static magnetic susceptibility measurements. Ferromagnetic resonance became to be observed at the particle size larger than 3.4 nm. This finding suggests that the bulk-like ferromagnetic state cannot be formed in the particle less than 3.4 nm diameter for magnetite. Magnetic moments in such a small diameter region were also determined by the analyses of magnetization curves and were found to be smaller than those expected from the particle size. These findings from ESR and magnetization are discussed to clarify the nature of spin-ordering in a finite size sample.     

Polyol合成法制备生物医药用超小粒径Fe3O4磁性纳米晶体

采用一罐polyol合成法还原Fe（Ⅲ）乙酰丙酮化合物制备了粒径可调、单分散、直径5nm以下的磁性Fe3O4纳米晶体．其晶粒表面为所用聚合物表面活性剂PVP所包覆．运用透射电镜／高分辨透射电镜、X射线衍射、振动样品磁强计和超导量子干涉仪对其结构和性能进行了表征．结果表明所制得的Fe3O4磁性纳米晶体在室温下显示出优良的超顺磁性,且结晶度高、分散性好、化学性质稳定同时表面易修饰．磁滞回线的模型分析说明该Fe3O4纳米晶粒是磁性单畴．该法制得的超顺磁Fe3O4纳米晶粒在生物和医学领域具有重要的应用价值．     

Controlled synthesis of uniform and monodisperse upconversion core/mesoporous silica shell nanocomposites for bimodal imaging

Here we report the design and controlled synthesis of monodisperse and precisely size-controllable UCNP@mSiO(2) nanocomposites smaller than 50?nm by directly coating a mesoporous silica shell (mSiO(2)) on upconversion nanocrystals NaYF(4):Tm/Yb/Gd (UCNPs), which can be used as near-infrared fluorescence and magnetic resonance imaging (MRI) agents and a platform for drug delivery as well. Some key steps such as transferring hydrophobic UCNPs to the water phase by using cetyltrimethylammonium bromide (CTAB), removal of the excess amount of CTAB, and temperature-controlled ultrasonication treatment should be adopted and carefully monitored to obtain uniform upconversion core/mesoporous silica shell nanocomposites. The excellent performance of the core-shell-structured nanocomposite in near-infrared fluorescence and magnetic resonance imaging was also demonstrated.     

Development of high magnetization Fe3O4/polystyrene/silica nanospheres via combined miniemulsion/emulsion polymerization

Monodispersed, hydrophilic, superparamagnetic magnetic nanospheres with a high fraction of magnetite were synthesized by combining modified miniemulsion/emulsion polymerization and sol-gel technique for the first time. The surface of the nanospheres was coated by a silica layer with controlled thickness. Transmission electron microscopy experimental results showed well-proportioned, equal-sized, magnetite/polystyrene (Fe3O4/PS) nanospheres with a thin silica shell. Based on the TGA data, the fraction of magnetite in the Fe3O4/PS nanospheres core was estimated to be 80 wt %. Magnetization measurements indicated that the superparamagnetic nature of the nanospheres had high saturation magnetization of 40 emu/g at 300 K. The procedures of the novel synthesis are described in detail. Also discussed are the mechanisms of the novel combined miniemulsion/emulsion polymerization processes.     

In-situ synthesis of magnetic (NiFe2O4/CuO/FeO) nanocomposites

In-situ synthesis of magnetic nanocomposites with (NiFe₂O₄/CuO/FeO) crystal phases has been done using a sol-gel method by taking a non-stoichiometric composition of the precursors. The average particle size of the nanocomposites was calculated using X-ray diffraction (XRD) and high resolution tunneling electron microscope (HR-TEM) and it turns out to be ∼20 nm. The vibrating sample magnetometer (VSM) measurements demonstrate the ferromagnetic nature of the nanocomposites. The synthesized nanocomposite was used to prepare magnetic fluid using tetramethylammonium hydroxide as a surfactant and its stability in the solution was also discussed.     

Synthesis, redox, and magnetic properties of a neutral, mixed-valent heptanuclear manganese wheel with S = 27/2 high-spin ground state

Reaction of lithium tetrachloromanganate(II) with N-n-butyldiethanolamine H2L3 (3) in the presence of LiH leads to the formation of wheel-shaped, mixed-valent heptanuclear, neutral complex {MnII subset[MnII2MnIII4Cl6(L3)6]} (4). The manganese wheel crystallizes in the triclinic space group P as 4.2CHCl3 or 4.3THF when either diethyl ether or n-pentane was allowed to diffuse into solutions of 4 in chloroform or tetrahydrofuran. The oxidation states of each manganese ion in 4.2CHCl3 or 4.3THF were assigned on the basis of detailed symmetry, bond length, and charge considerations, as well as by the Jahn-Teller axial elongation observed for the manganese(III) ions, and were further supported by cyclic voltammetry. The analysis of the SQUID magnetic susceptibility data for complex 4.2CHCl3 showed that the intramolecular magnetic coupling of the manganese(II,III) ions is dominated by ferromagnetic exchange interactions. This results in an S = 27/2 ground-state multiplet at low magnetic field. At fields higher than 0.68 T, the energetically lowest state is given by the mS = 31/2 component of the S = 31/2 multiplet due to the Zeeman effect. The ligand-field-splitting parameters were determined by anisotropy SQUID measurements on single crystalline samples along the crystallographic x, y, and z axes (D = -0.055 K, E = 6.6 mK) and by high-frequency electron spin resonance measurements on a polycrystalline powder of 4.2CHCl3 (D = -0.068 K, E = 9.7 mK). The resulting barrier height for magnetization reversal amounts to U approximately 10 K. Finally, 2DEG Hall magnetization measurements revealed that 4.2CHCl3 shows single-molecule magnet behavior up to the blocking temperature of about 0.6 K with closely spaced steps in the hysteresis because of the quantum tunneling of the magnetization.     

Nanocomposites Fe2O3/SiO2-Preparation by Sol-Gel Method and Physical Properties

Magnetic nanocomposites γ-Fe₂O₃/silica were prepared by a one-step sol-gel method. The sol was prepared by TEOS (tetraethyl orthosilicate) acid hydrolysis in the presence of an iron salt soluble in methanol. After gelation and drying, the transparent samples were characterized after treatment at different temperatures. The particle size, observed by HR TEM, was in the range of 2–10 nm and depended on Fe-concentration and heating temperature. Magnetic measurements showed either a ferromagnetic or a superparamagnetic behaviour and could be explained by the particle size. The dependence of the magnetic behaviour on the particle size was also studied by Mössbauer spectroscopy. The samples in which the Fe₂O₃ particle size was approximately 10 nm showed magnetic splitting (sextet) at room temperature, while smaller particles (2–3 nm) showed this splitting only at the temperature of liquid helium. The optomagnetic properties of the samples were also measured (Kerr effect).     

Magneto-Optical Properties of Silica Gel Containing Magnetite Fine Particles

The magnetic composite materials that consist of transparent matrix and magnetic fine particles are expected to have large residual magnetization and coercive force because of their fine magnetic domain structure, and also to show magneto-optical effects. Silica gels containing magnetite (Fe₃O₄) fine particles were prepared by sol-gel method. The magnetic, optical and magneto-optical properties of the composites were investigated by measurements of magnetization curves, UV-visible spectra and Faraday rotation in visible range. The saturation magnetization of the composite was almost as same as that expected from the amount of magnetite fine particles in it. Although the composites had large and broad absorption at around 400 nm, they still maintained their transparency. The origins of decrement of transparency attributed to the optical absorption of magnetite and scattering due to magnetite fine particles. The whole composites showed positive Faraday rotation under external static magnetic field due to the large contribution of diamagnetic silica gel matrix. Magnetite contributed negative Faraday rotation with maximum at around 470–480 nm to the magneto-optical spectra of the composites.     

Preparation of fluoroalkyl end-capped oligomers/magnetite nanocomposites possessing a good dispersibility and stability

Fluoroalkyl end-capped vinylphosphonic acid cooligomers-encapsulated magnetite nanocomposites were prepared by the magnetization of aqueous ferric and ferrous ions in the presence of the corresponding fluorinated cooligomers and magnetic nanoparticles under alkaline conditions. These fluorinated cooligomers magnetic composites are nanometer size-controlled very fine particles and have a good dispersibility and stability in water and traditional organic solvents. These fluorinated nanocomposites were also applied to the surface modification of poly(methyl methacrylate) to exhibit a good oleophobicity imparted by fluorine on their surface. Fluoroalkyl end-capped 2-methacryloyloxyethanesulfonic acid oligomer-encapsulated magnetite nanocomposites and fluoroalkyl end-capped 2-acrylamide-2-methylpropanesulfonic acid oligomer-encapsulated magnetite nanocomposites were prepared in good isolated yields by the magnetization of iron chlorides in the presence of the corresponding oligomers and magnetic nanoparticles under similar conditions. Colloidal stability of these fluorinated nanocomposites thus obtained in water was demonstrated to become extremely higher than that of fluorinated vinylphosphonic acid cooligomers/magnetic nanocomposites.     

One-dimensional magnetic nanowires obtained by protein fibril biotemplating

Magnetic nanowires were obtained through the in situ synthesis of magnetic material by Fe-controlled nanoprecipitation in the presence of two different protein (human serum albumin (HSA) and lysozyme (Lys)) fibrils as biotemplating agents. The structural characteristics of the biotemplates were transferred to the hybrid magnetic wires. They exhibited excellent magnetic properties as a consequence of the 1D assembly and fusion of magnetite nanoparticles as ascertained by SQUID magnetometry. Prompted by these findings, we also checked their potential applicability as MRI contrast agents. The magnetic wires exhibited large r(2)* relaxivities and sufficient contrast resolution even in the presence of an extremely small amount of Fe in the magnetic hybrids, which would potentially enable their use as T(2) contrast imaging agents.     

New Synthesis and Magnetic Properties of NiFe2O4/SiO2 and Co0.5Zn0.5Fe2O4/SiO2 Nanocomposites Using Tetraglycolatosilane as Precursor

In this work the new synthesis and magnetic properties of NiFe₂O₄/SiO₂ and Co_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites using a water‐soluble silica precursor, tetraglycolatosilane (THEOS), by the sol‐gel method were reported. Nanocomposite were obtained by the thermal decomposition of the organic part at different annealing temperatures varying from 400 to 900 °C. Studies carried out using XRD, FT‐IR, TEM, STA (TG‐DTG‐DTA) and VSM techniques. XRD patterns show that NiFe₂O₄ and Co_0.5Zn_0.5Fe₂O₄ have been formed in an amorphous silica matrix at annealing temperatures above 600 and 400 °C, respectively. It is found that when the annealing temperature is up to 900 °C NiFe₂O₄/SiO₂ and Co_0.5Zn_0.5Fe₂O₄/SiO₂ samples show almost superparamagnetic behavior with a magnetization 4.66 emu/g and ferromagnetic behavior with a magnetization 10.11 emu/g, respectively. The magnetization and coercivity values of nanocomposites using THEOS were considerably less than previous reports using TEOS. THEOS as a silica matrix network provides an ideal nucleation environment to disperse ferrite nanoparticles and thus to confine them to aggregate and coarsen. By using THEOS over the currently used TEOS and TMOS, organic solvents are not needed due to the entire solubility of THEOS in water. Synthesized nanocomposites with adjustable particle sizes and controllable magnetic properties make the applicability of ferrites even more versatile.     

Reactivity of metal-containing monomers 70. Preparation and magnetic properties of metal-containing nanocomposites

Nanocomposites containing magnetically active nanoparticles stabilized by the carbon-containing matrix formed in parallel were obtained by the polymerization—destruction synthesis. The composition, structure, and magnetic properties of nanocomposites synthesized by the thermal decomposition of unsaturated metal carboxylates and transition metal (Co^II, Ni^II, Fe^III) acrylamide complexes were studied by powder X-ray diffraction, scanning and transmission electron microscopy, and Mössbauer spectroscopy. The key macro stages and kinetic features of thermolysis of the metal-containing monomers were identified. The variation of the conditions of thermal transformations allows one to control the magnetic properties of nanocomposites from ferromagnetic to superparamagnetic behavior.

     

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.     

Monodispersed core-shell Fe3O4@Au nanoparticles

The ability to synthesize and assemble monodispersed core-shell nanoparticles is important for exploring the unique properties of nanoscale core, shell, or their combinations in technological applications. This paper describes findings of an investigation of the synthesis and assembly of core (Fe(3)O(4))-shell (Au) nanoparticles with high monodispersity. Fe(3)O(4) nanoparticles of selected sizes were used as seeding materials for the reduction of gold precursors to produce gold-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@Au). Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, core-shell composition, surface reactivity, and magnetic properties have confirmed the formation of the core-shell nanostructure. The interfacial reactivity of a combination of ligand-exchanging and interparticle cross-linking was exploited for molecularly mediated thin film assembly of the core-shell nanoparticles. The SQUID data reveal a decrease in magnetization and blocking temperature and an increase in coercivity for Fe(3)O(4)@Au, reflecting the decreased coupling of the magnetic moments as a result of the increased interparticle spacing by both gold and capping shells. Implications of the findings to the design of interfacial reactivities via core-shell nanocomposites for magnetic, catalytic, and biological applications are also briefly discussed.     

PLD-assisted VLS growth of aligned ferrite nanorods, nanowires, and nanobelts-synthesis, and properties

We report here a systematic synthesis and characterization of aligned alpha-Fe2O3 (hematite), epsilon-Fe2O3, and Fe3O4 (magnetite) nanorods, nanobelts, and nanowires on alumina substrates using a pulsed laser deposition (PLD) method. The presence of spherical gold catalyst particles at the tips of the nanostructures indicates selective growth via the vapor-liquid-solid (VLS) mechanism. Through a series of experiments, we have produced a primitive "phase diagram" for growing these structures based on several designed pressure and temperature parameters. Transmission electron microscopy (TEM) analysis has shown that the rods, wires, and belts are single-crystalline and grow along <111>m or <110>h directions. X-ray diffraction (XRD) measurements confirm phase and structural analysis. Superconducting quantum interference device (SQUID) measurements show that the iron oxide structures exhibit interesting magnetic behavior, particularly at room temperature. This work is the first known report of magnetite 1D nanostructure growth via the vapor-liquid-solid (VLS) mechanism without using a template, as well as the first known synthesis of long epsilon-Fe2O3 nanobelts and nanowires.     

FeCo/C nanocomposites: Synthesis,magnetic and electromagnetic properties

FeCo alloy nanoparticles encapsulated in the carbon matrix of metal–carbon nanocomposites have been manufactured under IR heating. The size of FeCo nanoparticles have been found to be tailored by varying synthesis temperature and metal concentration. The saturation magnetization has been shown to increase as the synthesis temperature or metal concentration rises, with an attendant decrease in coercive force. The electromagnetic properties of FeCo/C nanocomposites have been studied. Complex magnetic permittivity measurements have shown that variation of the synthesis temperature or metal concentration can appreciably increase magnetic loss, which leads to a shift of the band of minimum electromagnetic reflectivity in the frequency range 3–12 GHz.     

Effect of varying the acid to metal ion ratio R on the structural and magnetic properties of SiO2-doped Ni-Zn ferrite

A nitrate-citrate-silica gel was prepared from metallic nitrates, citric acid and tetraethoxysilane (TEOS) by sol-gel process with different citric acid to metal nitrates ratio R, and it was further used to synthesize Ni_0.5Zn_0.5Fe₂O₄/20 wt% SiO₂ nanocomposites by auto-combustion. The effect of varying the citric acid to metal nitrates ratio R on the structural and magnetic properties of the composites were studied by IR, ²⁹Si CP/MAS NMR, XRD, EPR and SQUID measurements. The nitrate-citrate-silica gels exhibited self-propagating combustion behavior, and it directly transformed into nanosized (14-22 nm) NiZn ferrite particles with spinel crystal structure after combustion. The R value in the starting solution affects the magnetic interaction between NiZn ferrite and silica, and then determines the particle size. Further, varying the R value has a direct effect on the EPR parameters (ΔH_PP, g factor, N_S and T₂) and SQUID parameters (M_s, M_r and H_c) of the as-synthesized powder.