Fe3O4 magnetic nanoparticles as peroxidase mimetics and their applications in H2O2 and glucose detection

Artificial enzyme mimetics are a current research interest because natural enzymes bear some serious disadvantages, such as their catalytic activity can be easily inhibited and they can be digested by proteases. A very recently study reported by Yan et al. has proven that Fe3O4 magnetic nanoparticles (MNPs) exhibit an intrinsic enzyme mimetic activity similar to that found in natural peroxidases, though MNPs are usually thought to be biological and chemical inert (Gao, L. Z.; Zhuang, J.; Nie, L.; Zhang, J. B.; Zhang, Y.; Gu, N.; Wang, T. H.; Feng, J.; Yang, D. L.; Perrett, S.; Yan, X. Y. Nat. Nanotechnol. 2007, 2, 577-583).

One-pot green synthesis of biocompatible arginine-stabilized magnetic nanoparticles

A green one-step approach has been developed for the synthesis of amino-functionalized magnetite nanoparticles. The synthesis was accomplished by simply mixing FeCl2 with arginine under ambient conditions. It was found that the Fe2+/arginine molar ratio, reaction duration and temperature greatly influence the size, morphology and composition of magnetic nanoparticles. The arginine-stabilized magnetic nanoparticles were characterized by transmission electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy techniques.

The interaction of polymer-coated magnetic nanoparticles with seawater

Laboratory studies were conducted to evaluate the interaction between bare and polymer-coated magnetic nanoparticles (MNPs) with various environmentally relevant carrying solutions including natural oceanic seawater with and without addition of algal exopolymeric substances (EPS). The MNPs were coated with three different stabilising agents, namely gum Arabic (GA-MNP), dextran (D-MNP) and carboxymethyl-dextran (CMD-MNP). The colloidal stability of the suspensions was evaluated over 48 h and we demonstrated that: (i) hydrodynamic diameters increased over time regardless of carrying solution for all MNPs except the GA-coated ones; however, the relative changes were carrying solution- and coat-dependent; (ii) polydispersity indexes of the freshly suspended MNPs are below 0.5 for all coated MNPs, unlike the much higher values obtained for the uncoated MNPs; (iii) freshly prepared MNP suspensions (both coated and uncoated) in Milli-Q (MQ) water show high colloidal stability as indicated by zeta-potential values below -30 mV, which however decrease in absolute value within 48 h for all MNPs regardless of carrying solution; (iv) EPS seems to "stabilise" the GA-coated and the CMD-coated MNPs, but not the uncoated or the D-coated MNPs, which form larger aggregates within 48 h; (v) despite this aggregation, iron (Fe)-leaching from MNPs is sustained over 48 h, but remained within the range of 3-9% of the total iron-content of the initially added MNPs regardless of suspension media and capping agent. The environmental implications of our findings and biotechnological applicability of MNPs are discussed.

Surface Functionalization of Monodisperse Magnetic Nanoparticles

We present a systematic methodology to functionalize magnetic nanoparticles through surface-initiated atom-transfer radical polymerization (ATRP). The magnetite nanoparticles are prepared according to the method proposed by Sun et al. (2004), which leads to a monodisperse population of ~ 6 nm particles stabilized by oleic acid. The functionalization of the nanoparticles has been performed by transforming particles into macro-initiators for the ATRP, and to achieve this two different routes have been explored. The first one is the ligand-exchange method, which consists of replacing some oleic acid molecules adsorbed on the particle surface with molecules that act as an initiator for ATRP. The second method consists in using the addition reaction of bromine to the oleic acid double bond, which turns the oleic acid itself into an initiator for the ATRP. We have then grown polymer brushes of a variety of acrylic polymers on the particles, including polyisopropylacrylamide and polyacrylic acid. The nanoparticles so functionalized are water soluble and show responsive behavior: either temperature responsive behavior when polyisopropylacrylamide is grown from the surface or PH responsive in the case of polyacrylic acid. This methodology has potential applications in the control of clustering of magnetic nanoparticles.

Synthesis and Characterization of Magnetic Nanoparticles with High Magnetization and Good Oxidation Resistibility

Magnetic nanoparticles attract increasing attention because of their current and potential biomedical applications, such as, magnetically targeted and controlled drug delivery, magnetic hyperthermia and magnetic extraction. Increased magnetization can lead to improved performance in targeting and retention in drug delivery and a higher efficiency in biomaterials extraction. We reported an approach to synthesize iron contained magnetic nanoparticles with high magnetization and good oxidation resistibility by pyrolysis of iron pentacarbonyl (Fe(CO)[subscript 5]) in methane (CH[subscript 4]). Using the high reactivity of Fe nanoparticles, decomposition of CH[subscript 4] on the Fe nanoparticles leads to the formation of nanocrystalline iron carbides at a temperature below 260°C. Structural investigation indicated that the as-synthesized nanoparticles contained crystalline bcc Fe, iron carbides and spinel iron oxide. The Mössbauer and DSC results testified that the as-synthesized nanoparticle contained three crystalline iron carbide phases, which converted to Fe[subscript 3]C after a heat treatment. Surface analysis suggested that the as-synthesized and subsequently heated iron-iron carbide particles were coated by iron oxide, which originated from oxidization of surface Fe atoms. The heat-treated nanoparticles exhibited a magnetization of 160 emu/g, which is two times of that of currently used spinel iron oxide nanoparticles. After heating in an acidic solution with a pH value of 5 at 60°C for 20 h, the nanoparticles retained 90 percentage of the magnetization.

Immobilisation of phenanthroline-bis triazine(c1-btphen) on magnetic nanoparticles for co-extraction of americium(III) and europium(III)

The present work reports a convenient route for the immobilisation of a phenanthroline-bis triazine (C1-BTPhen) group on the surface of zirconia-coated maghemite (γ-Fe2O3) magnetic nanoparticles. The magnetic nanoparticles functionalized with C1-BTPhen were able to co-extract Am(III) and Eu(III) from nitric acid (HNO3). The extraction efficiency of these C1-BTPhen-functionalized magnetic nanoparticles for both Am(III) and Eu(III) was 20% at 4M HNO3. The interaction between C1-BTPhen and metal cations is reversible. These functionalized magnetic nanoparticles can be used for the co-extraction of traces of Am(III) and Eu(III).

Neocuproine-functionalized silica-coated magnetic nanoparticles for extraction of copper(II) from aqueous solution

Neocuproine has been covalently bound to silica-coated maghemite(c-Fe2O3) magnetic nanoparticles (MNPs) by a phenyl ether linkage. The resulting MNPs are able to remove Cu(II) from 12 ppm aqueous solution with an extraction efficiency of up to 99% at pH 2.

Effective separation of Am(III) and Eu(III) from HNO3 Q1 Q2 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

Effective separation of Am(III) and Eu(III) from HNO3 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

The effect of DMSA-functionalized magnetic nanoparticles on transendothelial migration of monocytes in the murine lung via a beta(2) integrin-dependent pathway

Magnetic nanoparticles surface-functionalized with meso-2,3-dimercaptosuccinic acid (MNPs-DMSA) constitute an innovative and promising approach for tissue- and cell-targeted delivery of therapeutic drugs in the lung. Transendothelial migration of leukocytes in the lung is a side effect of endovenous administration of MNPs-DMSA. Using cytologic and phenotypic analysis of murine bronchoalveolar lavage cells, we identified monocytes/macrophages as the main subpopulation of leukocytes involved in this process. Moreover, ultrastructural analysis revealed the presence of nanoparticles inside of numerous macrophages from bronchoalveolar lavage. MNPs-DMSA at concentrations as high as 1 X 10(15) nanoparticles/mL had no toxic effects on macrophages, as evidenced by 3-(4, 5-dimethylthiazolyi-2)-2,5-diphenyltetrazolium bromide (MTT) assay. Notably, MNPs-DMSA up-regulated the mRNA expression of E, L- and P-selectin and macrophage-1 antigen in the murine lung. Upregulation of these cell adhesion molecules was associated with an increased concentration of tumor necrosis factor-alpha in lung. Finally, the critical relevance of the beta(2) integrin-dependent pathway in leukocyte transmigration elicited by MNPs-DMSA was demonstrated by use of knockout mice. Our results characterize mechanisms of the pro-inflammatory effects of MNPs-DMSA in the lung, and identify beta(2) integrin-targeted interventions as promising strategies to reduce pulmonary side effects of MNPs-DMSA during biomedical applications. (C) 2009 Elsevier Ltd. All rights reserved.

Application of computed tomography images in the evaluation of magnetic nanoparticles biodistribution

In this work we evaluate the effectiveness of computed tomography images as a tool to determine magnetic nanoparticle biodistribution over biological tissues. For this purpose, tomography images for magnetic nanoparticles, composed of Fe(3)O(4), coated with 2,3-dimercaptosuccinic acid (DMSA), were generated at several material concentrations. The comparison of CT numbers, calculated from these images generated at clinical conditions, with typical CT numbers for biological tissues, shows that the detection of nanoparticle in most tissues is only possible for high material concentrations. (C) 2010 Elsevier B.V. All rights reserved.

Aerobic oxidation of monoterpenic alcohols catalyzed by ruthenium hydroxide supported on silica-coated magnetic nanoparticles

Ruthenium hydroxide supported on silica-coated magnetic nanoparticles was shown to be an efficient heterogeneous catalyst for the liquid-phase oxidation of a wide range of alcohols using molecular oxygen as a sole oxidant in the absence of co-catalysts or additives. The material was prepared through the loading of the amino modified support with ruthenium(III) ions from an aqueous solution of ruthenium(III) chloride followed by treatment with sodium hydroxide to form ruthenium hydroxide species. Characterizations suggest that ruthenium hydroxide is highly dispersed on the support surface, with no ruthenium containing crystalline phases being detected. Various carbonylic monoterpenoids important for fragrance and pharmaceutical industries can be obtained in good to excellent yields starting from biomass-based monoterpenic alcohols, such as isobomeol, perillyl alcohol, carveol, and citronellol. The catalyst undergoes no metal leaching and can be easily recovered by the application of an external magnet and re-used. (C) 2011 Elsevier Inc. All rights reserved.

Magnet-induced temporary superhydrophobic coatings from one-pot synthesized hydrophobic magnetic nanoparticles.

In this paper, we report on the production of superhydrophobic coatings on various substrates (e.g., glass slide, silicon wafer, aluminum foil, plastic film, nanofiber mat, textile fabrics) using hydrophobic magnetic nanoparticles and a magnet-assembly technique. Fe3O4 magnetic nanoparticles functionalized with a thin layer of fluoroalkyl silica on the surface were synthesized by one-step coprecipitation of Fe2+/Fe3+ under an alkaline condition in the presence of a fluorinated alkyl silane. Under a magnetic field, the magnetic nanoparticles can be easily deposited on any solid substrate to form a thin superhydrophobic coating with water contact angle as high as 172°, and the surface superhydrophobicity showed very little dependence on the substrate type. The particulate coating showed reasonable durability because of strong aggregation effect of nanoparticles, but the coating layer can be removed (e.g., by ultrasonication) to restore the original surface feature of the substrates. By comparison, the thin particle layer deposited under no magnetic field showed much lower hydrophobicity. The main reason for magnet-induced superhydrophobic surfaces is theformation of nano- and microstructured surface features. Such a magnet-induced temporary superhydrophobic coating may have wide applications in electronic, biomedical, and defense-related areas.

Magneto Immunoassays for Plasmodium falciparum Histidine-Rich Protein 2 Related to Malaria based on Magnetic Nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

High efficacy in hyperthermia-associated with polyphosphate magnetic nanoparticles for oral cancer treatment

Nanotherapy applied to cancer treatment is constantly evolving, and new approaches to current techniques, such as magnetohyperthermia, are being implemented to solve and minimize the limitations of conventional therapeutic strategies. The purpose of this study was to investigate the action of polyphosphate-coated maghemite nanoparticles (MNPs) on oral squamous cell carcinoma. Human oral cancer cells (UM-SCC14A) were incubated with MNPs at various concentrations and subjected to cell proliferation tests (MTT), apoptosis assays and transmission electron image analysis. Viability and apoptotic events were time and dose dependent. These in vitro tests showed that at the intermediate concentration tested there is no significant toxicity, as confirmed by transmission electron microscopy. For this reason this MNPs concentration was chosen for the subsequent in vivo tests. Oral tumor induction was performed by applying the carcinogen DMBA to Syrian hamsters. Animals were then treated by magnetohyperthermia using MNPs. No signs of general clinical symptoms of toxicity or abnormal behavioral reactions were observed. However, animals treated with MNPs and exposed to the alternating magnetic field in the hyperthermia procedure exhibited a significant and time dependent cancer regression, as confirmed by histopathological analyses and immunohistochemistry. Actually, in quantitative terms of the magnetotherapy efficacy involving these polyphosphate-coated MNPs, 100% recovery (12/12) was observed in the oral cancer tumor bearing Syrian hamsters seven days after the treatment with the magnetohyperthermia procedure. Data supports the suggestion that the MNPs-mediated hyperthermia represents a promising strategy for the treatment of oral cancer.