In vivo magnetic resonance detection of cancer by using multifunctional magnetic nanocrystals

The unique properties of magnetic nanocrystals provide them with high potential as key probes and vectors in the next generation of biomedical applications. Although superparamagnetic iron oxide nanocrystals have been extensively studied as excellent magnetic resonance imaging (MRI) probes for various cell trafficking, gene expression, and cancer diagnosis, further development of in vivo MRI applications has been very limited. Here, we describe in vivo diagnosis of cancer, utilizing a well-defined magnetic nanocrystal probe system with multiple capabilities, such as small size, strong magnetism, high biocompatibility, and the possession of active functionality for desired receptors. Our magnetic nanocrystals are conjugated to a cancer-targeting antibody, Herceptin, and subsequent utilization of these conjugates as MRI probes has been successfully demonstrated for the monitoring of in vivo selective targeting events of human cancer cells implanted in live mice. Further conjugation of these nanocrystal probes with fluorescent dye-labeled antibodies enables both in vitro and ex vivo optical detection of cancer as well as in vivo MRI, which are potentially applicable for an advanced multimodal detection system. Our study finds that high performance in vivo MR diagnosis of cancer is achievable by utilizing improved and multifunctional material properties of iron oxide nanocrystal probes.     

Surface modulation of magnetic nanocrystals in the development of highly efficient magnetic resonance probes for intracellular labeling

High-quality biocompatible magnetic iron oxide (Fe3O4) nanocrystals were developed through a ligand exchange process of hydrophobically capped nanocrystals with hydrophilic molecules. By simple modulation of the nanocrystal surface ligand charge properties, we have been able to prepare magnetic nanocrystals with excellent intracellular labeling capabilities that efficiently label a variety of cell types without the need for additional transport facilitating agents. The excellent intracellular labeling capability of the newly developed cationic WSIO has further led to successful MRI monitoring of the migration of neural stem cells in rat spinal cord. The magnetic nanocrystals developed here have great potential in applications for labeling of various cell types and also the monitoring of cell-based medical treatments and cancer metastasis.     

Shape control and associated magnetic properties of spinel cobalt ferrite nanocrystals

By combining nonhydrolytic reaction with seed-mediated growth, high-quality and monodisperse spinel cobalt ferrite, CoFe(2)O(4), nanocrystals can be synthesized with a highly controllable shape of nearly spherical or almost perfectly cubic. The shape of the nanocrystals can also be reversibly interchanged between spherical and cubic morphology through controlling nanocrystal growth rate. Furthermore, the magnetic studies show that the blocking temperature, saturation, and remanent magnetization of nanocrystals are solely determined by the size regardless the spherical or cubic shape. However, the shape of the nanocrystals is a dominating factor for the coercivity of nanocrystals due to the effect of surface anisotropy. Such magnetic nanocrystals with distinct shapes possess tremendous potentials in fundamental understanding of magnetism and in technological applications of magnetic nanocrystals for high-density information storage.     

Stable photogenerated carriers in magnetic semiconductor nanocrystals

We report the preparation and investigation of charged colloidal Co2+:ZnO and Mn2+:ZnO nanocrystals. Although both charged and magnetically doped colloidal semiconductor nanocrystals have been reported previously, colloidal charged and magnetically doped semiconductor nanocrystals as described herein have not. Conduction band electrons were introduced into colloidal ZnO diluted magnetic semiconductor (DMS) nanocrystals photochemically, and the resulting TM2+-e-CB interactions were observed by electron paramagnetic resonance spectroscopy (TM2+ = Co2+ or Mn2+). This new motif of colloidal charged magnetic semiconductor nanocrystals reveals attractive new opportunities for studying spin effects in DMS nanostructures relevant to proposed spintronics technologies.     

Magnetic, electronic, and structural characterization of nonstoichiometric iron oxides at the nanoscale

We have investigated the structural, magnetic, and electronic properties of nonstoichiometric iron oxide nanocrystals prepared by decomposition of iron(II) and iron(0) precursors in the presence of organic solvents and capping groups. The highly uniform, crystalline, and monodisperse nanocrystals that were produced enabled a full structural and compositional survey by electron microscopy and X-ray diffraction. The complex and metastable behavior of nonstoichiometric iron oxide (wüstite) at the nanoscale was studied by a combination of Mossbauer spectroscopy and magnetic characterization. Deposition from hydrocarbon solvents with subsequent self-assembly of iron oxide nanocrystals into superlattices allowed the preparation of continuous thin films suitable for electronic transport measurements.     

Copper oxide nanocrystals

It is well-known that inorganic nanocrystals are a benchmark model for nanotechnology, given that the tunability of optical properties and the stabilization of specific phases are uniquely possible at the nanoscale. Copper (I) oxide (Cu(2)O) is a metal oxide semiconductor with promising applications in solar energy conversion and catalysis. To understand the Cu/Cu(2)O/CuO system at the nanoscale, we have developed a method for preparing highly uniform monodisperse nanocrystals of Cu(2)O. The procedure also serves to demonstrate our development of a generalized method for the synthesis of transition metal oxide nanocrystals. Cu nanocrystals are initially formed and subsequently oxidized to form highly crystalline Cu(2)O. The volume change during phase transformation can induce crystal twinning. Absorption in the visible region of the spectrum gave evidence for the presence of a thin, epitaxial layer of CuO, which is blue-shifted, and appears to increase in energy as a function of decreasing particle size. XPS confirmed the thin layer of CuO, calculated to have a thickness of approximately 5 A. We note that the copper (I) oxide phase is surprisingly well-stabilized at this length scale.     

Magnetic targeting and cellular uptake of polymer microcapsules simultaneously functionalized with magnetic and luminescent nanocrystals

By using a flow channel system for modeling the bloodstream in the circulatory system and by locally creating a magnetic field gradient caused by a permanent magnet, we demonstrate specific trapping of polymer capsules simultaneously functionalized with two types of nanoparticles--magnetic and luminescent nanocrystals. In the regions where the capsules were trapped by the magnetic field, drastically increased uptake of capsules by cells has been observed. The uptake of capsules by cells could be conveniently monitored with a fluorescence microscope by the luminescence of CdTe nanocrystals that had been embedded into the shells of the capsules. Our experiments envisage the feasibility of magnetic targeting of polymer capsules loaded by pharmaceutical agents to pathogenic parts of a tissue.     

Architectural control of magnetic semiconductor nanocrystals.

Shape- and dopant-controlled magnetic semiconductor nanocrystals have been achieved by the thermolysis of nonpyrophoric and less reactive single molecular precursors under a monosurfactant system. Reaction parameters governing both the intrinsic crystalline phase and the growth regime (kinetic vs thermodynamic) are found to be important for the synthesis of various shapes of MnS nanocrystals that include cubes, spheres, 1-dimensional (1-D) monowires, and branched wires (bipods, tripods, and tetrapods). Obtained nanowires exhibit enhanced optical and magnetic properties compared to those of 0-D nanospheres. Proper choice of molecular precursors and kinetically driven low-temperature growth afford dopant controlled 1-D Cd1-xMn(x)S nanorods at high levels (up to approximately 12%) of Mn, which is supported by repeated surface exchange experiments and X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) analyses.     

Heterostructured magnetic nanoparticles: their versatility and high performance capabilities

Magnetic nanoparticles exhibit unique nanoscale properties and their utilization for various magnetic systems is of significant interest. Especially, heterostructured magnetic nanoparticles are emerging as next-generation materials due to their synergistically enhanced magnetism and potential multifunctionalities. Herein, we overview the recent advances in the development of magnetic nanoparticles with a focus on multicomponent heterostructured nanoparticles including alloys, core-shells, and binary superlattices synthesized via nonhydrolytic methods. Their multifunctionalites and high performance capabilities are demonstrated for applications in high density magnetic storages, chemical catalysis, and biomedical separation and diagnostics.     

Size dependence of the magnetic properties in ferrimagnetic rings MnxRx (x = 2–8)

Size dependence of the magnetic properties in nanoscale ferrimagnetic rings is investigated by the numerical diagonalization of the Heisenberg model. The field derivative of the magnetization is drastically dependent on size of the ring if the magnetic system has frustration, although the character does not exist in the non-frustrated system. Our numerical data support this tendency that the effect of frustration causes the size dependence of the magnetic properties in the nanoscale ferrimagnetic ring. We also demonstrate that the size dependence caused by frustration is also found in behavior of the translational quantum number of the ground state.     

Seven-nanometer hexagonal close packed cobalt nanocrystals for high-temperature magnetic applications through a novel annealing process

Seven-nanometer cobalt nanocrystals are synthesized by colloidal chemistry. Gentle annealing induces a direct structural transition from a low crystalline state to the hexagonal close packed (hcp) phase without changing the size, size distribution, and the lauric acid passivating layer. The hcp structured nanocrystals can be easily redispersed in solvent for further application and processing. We found that the magnetization at saturation and the magnetic anisotropy are strongly modified through the annealing process. Monolayer self-assembly of the hcp cobalt nanocrystals is obtained, and due to the dipolar interaction, ferromagnetic behavior close to room temperature has been observed. This work demonstrates a novel approach for obtaining small size hcp structured cobalt magnetic nanocrystals for many technological applications.     

First synthesis by liquid-liquid phase transfer of magnetic CoxPt100-x nanoalloys

Controlled synthesis of magnetic nanoparticles with a well-known size and composition is always a challenge. A soft chemical synthesis was developed to obtain magnetic alloy nanocrystals with a high ability to control composition, size, and polydispersity. Cobalt-platinum alloy nanocrystals were synthesized using a colloidal approach by the liquid-liquid phase transfer method. Structural characterization using HRTEM and XRD was carried out on nanocrystals in the range of 25-75% cobalt composition, which indicated the formation of nanoalloy bimetallic CoxPt100-x. Adjusting the alkylamine capping agent and the kinetics of the reduction process allowed tuning of the size in the range of 1.8-4 nm while keeping an equiatomic composition. The narrow size distribution led to the possibility of inducing nanoparticle self-organization over a long range. The magnetic properties of the Co50Pt50 nanoalloy in the disordered face-centered cubic phase A1 were studied for different nanoparticle sizes.     

Study of nucleation and growth in the organometallic synthesis of magnetic alloy nanocrystals: the role of nucleation rate in size control of CoPt3 nanocrystals

High quality CoPt(3) nanocrystals were synthesized via simultaneous reduction of platinum acetylacetonate and thermodecomposition of cobalt carbonyl in the presence of 1-adamantanecarboxylic acid and hexadecylamine as stabilizing agents. The high flexibility and reproducibility of the synthesis allows us to consider CoPt(3) nanocrystals as a model system for the hot organometallic synthesis of metal nanoparticles. Different experimental conditions (reaction temperature, concentration of stabilizing agents, ratio between cobalt and platinum precursors, etc.) have been investigated to reveal the processes governing the formation of the metal alloy nanocrystals. It was found that CoPt(3) nanocrystals nucleate and grow up to their final size at an early stage of the synthesis with no Ostwald ripening observed upon further heating. In this case, the nanocrystal size can be controlled only via proper balance between the rates for nucleation and for growth from the molecular precursors. Thus, the size of CoPt(3) nanocrystals can be precisely tuned from approximately 3 nm up to approximately 18 nm in a predictable and reproducible way. The mechanism of homogeneous nucleation, evolution of the nanocrystal ensemble in the absence of Ostwald ripening, nanocrystal faceting, and size-dependent magnetic properties are investigated and discussed on the example of CoPt(3) magnetic alloy nanocrystals. The developed approach was found to be applicable to other systems, e.g., FePt and CoPd(2) magnetic alloy nanocrystals.     

Enhancement of magnetic resonance contrast effect using ionic magnetic clusters

Precise diagnosis by magnetic resonance imaging (MRI) requires sensitive magnetic resonance probes to detect low concentrations of magnetic substances. Ionic magnetic clusters (IMCs) as versatile magnetic probes were successfully synthesized for enhancing the magnetic resonance (MR) contrast effect as well as ensuring high water solubility. IMCs with various sizes were prepared by assembly of MNCs using cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS). To synthesize IMCs in the aqueous phase, magnetic nanocrystals in an organic solvent were assembled with CTAB and SDS using the nanoemulsion method, to fabricate cationic magnetic clusters (CMCs) and anionic magnetic clusters (AMCs), respectively. IMCs demonstrated ultrasensitivity by MR imaging and sufficient magnetic mobility under an external magnetic field.     

Controlled synthesis and magnetic properties of bimagnetic spinel ferrite CoFe2O4 and MnFe2O4 nanocrystals with core-shell architecture

A combination of hard phase CoFe(2)O(4) and soft phase MnFe(2)O(4) as the bimagnetic nanocrystals in a core-shell architecture has been synthesized, and their magnetic properties have been systematically studied. Both HRTEM and EDS results confirmed the formation of bimagnetic core-shell structured nanocrystals. On the basis of the systematic and comparative studies of the magnetic properties of a mechanical mixture of pure CoFe(2)O(4) and MnFe(2)O(4) nanocrystals, chemically mixed Co(1-x)Mn(x)Fe(2)O(4) nanocrystals, and bimagnetic core-shell CoFe(2)O(4)@MnFe(2)O(4) and MnFe(2)O(4)@CoFe(2)O(4) nanocrystals, the bimagnetic core-shell nanocrystals show very unique magnetic properties, such as the blocking temperature and coercivity. Our results show that the coercivity correlates with the volume fraction of the soft phase as the theoretical hard-soft phase model has suggested. Furthermore, switching the hard phase CoFe(2)O(4) from the core to the shell shows great changes in the coercivity of the nanocrystals. The bimagnetic core-shell nanocrystals evidently demonstrate the rational design capability to separately control the blocking temperature and the coercivity in magnetic nanocrystals by varying the materials, their combination, and the volume ratio between the core and the shell and by switching hard or soft phase materials between the core and shell. Such controls via a bimagnetic core-shell architecture are highly desirable for magnetic nanocrystals in various applications.     

One-pot synthesis of highly monodispersed ferrite nanocrystals: surface characterization and magnetic properties

In the present study, a facile one-pot synthetic route, utilizing a strong polar organic solvent, N-methyl 2-pyrrolidone (NMP), is demonstrated to obtain highly monodispersed ferrite nanocrystals. The equimolar mixture of oleic acid, C(17)H(33)COOH (R-COOH), and oleylamine, C(18)H(35)NH(2) (R'-NH(2)), was used to coat the magnetic nanocrystals. Structural and magnetic properties of the ferrite nanocrystals were studied by a multitechnique approach including X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), and M?ssbauer spectroscopy. FTIR spectral analysis indicates oleylamine helps in deprotonation of oleic acid, resulting in the formation of an acid-base complex, R-COOˉ:NH(3)(+)-R', which acts as binary capping agent. Structural and coordination differences of iron were studied by XPS and M?ssbauer spectral analysis. XPS analysis was carried out to examine the oxidation state of iron ions in iron oxide nanocrystals. The presence of a magnetically dead layer (～0.38 and ～0.67 nm) and a nonmagnetic organic coating (～2.3 and ～1.7 nm) may substantially reduce the saturation magnetization values for CoFe(2)O(4) and Fe(3)O(4) nanocrystals, respectively. The energy barrier distribution function of magnetic anisotropy was derived from the temperature dependent decay of magnetization. A very narrow energy barrier distribution elucidates that the ferrite nanocrystals obtained in this study are highly monodispersed.     

Luminescent polymer microcapsules addressable by a magnetic field

The simultaneous encapsulation of both luminescent semiconductor and magnetic oxide nanoparticles in polymer microcapsules is demonstrated for the first time. Highly luminescent CdTe semiconductor nanocrystals serve as luminescent markers, while magnetic Fe3O4 nanoparticles allow external manipulation of the capsules by magnetic field. The method introduced is general enough to allow the fabrication of different types of multifunctional capsules in a similar way. The use of multifunctional water-compatible capsules introduced in this paper for the controlled release and directed drug delivery in biological systems is envisaged.     

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.     

Nature of catalytic activities of CoO nanocrystals in thermal decomposition of ammonium perchlorate

This work addresses the chemical nature of the catalytic activity of X-ray "pure" CoO nanocrystals. All samples were prepared by a solvothermal reaction route. X-ray diffraction indicates the formation of CoO in a cubic rock-salt structure, while infrared spectra and magnetic measurements demonstrate the coexistence of CoO and Co 3O 4. Therefore, X-ray "pure" CoO nanocrystals are a unique composite structure with a CoO core surrounded by an extremely thin Co 3O 4 surface layer, which is likely a consequence of the surface passivation of CoO nanocrystals from the air oxidation at room temperature. The CoO core shows a particle size of 22 or 280 nm, depending on the types of the precursors used. This composite nanostructure was initiated as a catalytic additive to promote the thermal decomposition of ammonium perchlorate (AP). Our preliminary investigations indicate that the maximum decomposition temperature of AP is significantly reduced in the presence of CoO/Co 3O 4 composite nanocrystals and that the maximum decomposition peak shifts toward lower temperatures as the loading amount of the composite nanocrystals increases. These findings are different from the literature reports when using many nanoscale oxide additives. Finally, the decomposition heat for the low-temperature decomposition stages of AP was calculated and correlated to the chemical nature of the CoO/Co 3O 4 composite nanostructures.     

Synthesis and magnetic properties of colloidal MnPt3 nanocrystals

The colloidal synthesis and magnetic properties of MnPt(3) nanocrystals are reported. The nanocrystal size depended on the Mn reactant used, but the Mn:Pt stoichiometry was always 1:3. As synthesized, the nanocrystals are compositionally disordered with the face-centered cubic (fcc) A1 phase. Annealing at 580 degrees C changed the MnPt(3) crystal structure to the compositionally ordered L1(2) phase (AuCu(3) structure) with higher magnetocrystalline anisotropy. Magnetization measurements showed that the A1 nanocrystals are paramagnetic and the L1(2) MnPt(3) nanocrystals are superparamagnetic.