Fe3O4磁性纳米颗粒的合成与接枝聚合修饰（英文）

以氨水作为沉淀剂并控制溶液的pH值,采用Fe3+和Fe2+共沉淀法制得了磁性四氧化三铁纳米颗粒。合成的磁性纳米颗粒通过高分辨透射电镜、X射线衍射仪、傅里叶变换红外光谱仪进行了表征。四氧化三铁纳米颗粒的粒径约为10nm,其表面含有丰富的羟基。为了增强磁性四氧化三铁纳米颗粒和聚合物基质之间的相互作用,在纳米颗粒的表面接枝上乙烯基单体。傅里叶变换红外光谱仪和热重分析仪的测试结果显示,聚合物链共价结合在纳米颗粒表面。表面接枝聚合后,四氧化三铁纳米颗粒由极性转变为非极性。     

Catalase-imprinted Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Fe@fibrous SiO<Subscript>2</Subscript>/polydopamine nanoparticles: An integrated nanoplatform of magnetic targeting,magnetic resonance imaging,and dual-mode cancer therapy

Recent advances in the research on the molecular mechanism of cell death and methods for preparation of nanomaterials make the integration of various therapeutic approaches,targeting,and imaging modes into a single nanoscale complex a new trend for the development of future nanotherapeutics.Hence,a novel ellipsoidal composite nanoplatform composed of a magnetic Fe3O4/Fe nanorod core (～120 nm) enwrapped by a catalase (CAT)-imprinted fibrous SiO2/ polydopamine (F-SiO2/PDA) shell with thickness 70 nm was prepared in this work.In vitro experiments showed that the Fe3O4/Fe@F-SiO2/PDA nanoparticles can selectively inhibit the bioactivity of CAT in tumor cells by the molecular imprinting technique.As a result,the H2O2 level in tumor cells was elevated dramatically.At the same time,the Fe3O4/Fe core released Fe ions to catalyze the conversion of H2O2 to ·OH in tumor cells.Eventually,the concentration of ·OH in tumor cells rapidly rose to a lethal level thus triggering apoptosis.Combined with the remarkable near-infrared light (NIR) photothermal effect of the CATimprinted PDA layer,the Fe3O4/Fe@F-SiO2/PDA nanoparticles can effectively kill MCF-7,HeLa,and 293T tumor cells but are not toxic to nontumor cells.Furthermore,these nanoparticles show good capacity for magnetic targeting and suitability for magnetic resonance imaging (MRI).Therefore,the integrated multifunctional nanoplatform opens up new possibilities for high-efficiency visual targeted nonchemo therapy for cancer.     

Adsorption of Cd2+ on carboxyl-terminated superparamagnetic iron oxide nanoparticles

The affinity of Cd(2+) toward carboxyl-terminated species covalently bound to monodisperse superparamagnetic iron oxide nanoparticles, Fe(3)O(4)(np)-COOH, was investigated in situ in aqueous electrolytes using rotating disk electrode techniques. Strong evidence that the presence of dispersed Fe(3)O(4)(np)-COOH does not affect the diffusion limiting currents was obtained using negatively and positively charged redox active species in buffered aqueous media (pH = 7) devoid of Cd(2+). This finding made it possible to determine the concentration of unbound Cd(2+) in solutions containing dispersed Fe(3)O(4)(np)-COOH, 8 and 17 nm in diameter, directly from the Levich equation. The results obtained yielded Cd(2+) adsorption efficiencies of ~20 μg of Cd/mg of Fe(3)O(4)(np)-COOH, which are among the highest reported in the literature employing ex situ methods. Desorption of Cd(2+) from Fe(3)O(4)(np)-COOH, as monitored by the same forced convection method, could be accomplished by lowering the pH, a process found to be highly reversible.     

基于Pd/Fe3O4/rGO纳米复合材料的H2O2无酶传感器

环境监测、食品工业、临床、制药等领域对过氧化氢(H_2O_2)的快速、准确检测有极大的需求,而电化学检测方法由于灵敏度高、响应快、检测限低等特点被认为是最理想的H_2O_2检测方法.本文利用电化学沉积的方法将Pd纳米颗粒沉积到四氧化三铁/石墨烯(Fe_3O_4/rGO)纳米复合材料修饰的玻碳电极表面,形成基于新型磁性纳米复合材料的H_2O_2无酶传感器;并采用循环伏安和计时安培电流等方法对修饰电极的电化学性能进行了表征.结果表明:制备的Pd/Fe_3O_4/r GO/GCE对H_2O_2的催化还原显示出较好的电催化活性,Pd纳米颗粒和Fe_3O_4/rGO在催化H_2O_2还原的过程中表现出了良好的协同作用.测定H_2O_2的线性范围为0.05~1 m M和1~2.6 m M两段,最低检测限达到3.918μM(S/N=3).并且该传感器具有较高的灵敏度和较好的重现性和抗干扰性,具有一定的实际应用价值.     

Electrocatalytic reduction of H2O2 on thiolate graphene oxide covalently to bonded palladium nanoparticles

The electrocatalytic reduction of hydrogen peroxide on thioalted graphene oxide (t-GO) covalent bonded to palladium nanoparticles was used as the basis of an H2O2 biosensor. Poly (diallydimethylammonium chloride)-coated t-GO-Pd on glassy carbon electrodes was easily and quickly prepared and gave sensitive measurements of H2O2 concentration. The Pd nanoparticles covalently bonded to the thiolated graphene oxide were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Comparable results for H2O2 determination were obtained from cyclic voltammetric and amperometric measurements. The proposed H2O2 biosensor exhibited a wide linear range of 10 microM to 10 mM, and a low detection limit of 0.22 microM (S/N = 3), at an applied potential of -0.1 V by the amperometric method.     

Oxidative stress and apoptosis induced by iron oxide nanoparticles in cultured human umbilical endothelial cells

Recent epidemiologic researches indicate that exposure to ultrafine particles (nanoparticles) is an independent risk factor for several cardiovascular diseases. The induction of endothelial injuries is hypothesized to be an attractive mechanism involved in these cardiovascular diseases. To investigate this hypothesis, the widely used iron nanomaterials, ferric oxide (Fe2O3) and ferriferrous oxide (Fe3O4) nanoparticles were incubated with human umbilical endothelial cells (ECV304 cells) at different concentrations of 2, 20, 100 microg/mL. The cell viability, the rate of apoptosis, the apoptotic nuclear morphology and the mitochondria membrane potential were measured to estimate the cell necrosis and apoptosis caused by the nanoparticle exposure. The stimulation of superoxide anion (O2*-) and nitric oxide (NO) were examined to evaluate the stress responses of endothelial cells. Our results indicated that both the Fe2O3 and Fe3O4 nanoparticles could generate oxidative stress as well as the significant increase of nitric oxide in ECV304 cells. The loss of mitochondria membrane potential and the apoptotic chromatin condensation in the nucleus were observed as the early signs of apoptosis. It is inferred the stress response might be an important mechanism involving in endothelial cells apoptosis and death, and these injuries in endothelial cells might play a key role in downstream cardiovascular diseases such as atheroscelerosis, hypertension and myocardial infarction (MI).     

Synthesis and characterization of SiO2/(PMMA/Fe3O4) magnetic nanocomposites

Magnetic silica nanocomposites (magnetic nanoparticles core coated by silica shell) have the wide promising applications in the biomedical field and usually been prepared based on the famous St?ber process. However, the flocculation of Fe3O4 nanoparticles easily occurs during the silica coating, which limits the amount of magnetic silica particles produced in the St?ber process. In this paper, PMMA/Fe3O4 nanoparticles were used in the St?ber process instead of the "nude" Fe3O4 nanoparticles. And coating Fe3O4 with PMMA polymer beforehand can prevent magnetic nanoparticles from the aggregation that usually comes from the increasing of ionic strength during the hydrolyzation of tetraethoxysilane (TEOS) by the steric hindrance. The results show that the critical concentration of magnetic nanoparticles can increase from 12 mg/L for "nude" Fe3O4 nanoparticles to 3 g/L for PMMA/Fe3O4 nanoparticles during the St?ber process. And before the deposition of silica shell, the surface of PMMA/FeO4 nanoparticles had to be further modified by hydrolyzing them in CH3OH/NH3 x H2O mixture solution, which provides the carboxyl groups on their surface to react further with the silanol groups of silicic acid.     

Functional Fe3O4/TiO2 core/shell magnetic nanoparticles as photokilling agents for pathogenic bacteria

A photokilling approach for pathogenic bacteria is demonstrated using a new type of magnetic nanoprobe as the photokilling agent. In addition to their magnetic property, the nanoprobes have other features including a photocatalytic property and the capacity to target bacteria. The nanoprobes comprise iron oxide/titania (Fe(3)O(4)@TiO(2)) core/shell magnetic nanoparticles. As dopamine molecules can self-assemble onto the surface of the titania substrate, dopamine is used as the linker to immobilize succinic anhydride onto the surfaces of the Fe(3)O(4)@TiO(2) nanoparticles. This is followed by the immobilization of IgG via amide bonding. We demonstrate that the IgG-Fe(3)O(4)@TiO(2) magnetic nanoparticles not only have the capacity to target several pathogenic bacteria, but they also can effectively inhibit the cell growth of the bacteria targeted by the nanoparticles under irradiation of a low-power UV lamp within a short period. Staphylococcus saprophyticus, Streptococcus pyogenes, and antibiotic-resistant bacterial strains, such as multiantibiotic-resistant S. pyogenes and methicillin-resistant Staphylococcus aureus (MRSA), are used to demonstrate the feasibility of this approach.     

One-dimensional magnetopolymeric nanostructures with tailored sizes

Ultra-high aspect ratio nanofibers composed of poly(vinyl alcohol) and CoFe(2)O(4) nanoparticles (PVA/CoFe(2)O(4)) and moderate aspect ratio nanofibers composed of poly(vinyl chloride) and Fe(3)O(4) nanoparticles (PVC/Fe(3)O(4)) have been prepared. Magnetopolymeric one-dimensional (1D) nanostructures with any diameter and length can be prepared by template synthesis using anodic aluminum oxide (AAO) followed by the replication methods presented in this work. These replication methods are very effective, and allow the nanomoulding of any polymer-nanoparticle 1D composite. A first magnetic characterization of the nanostructured composites reveals a modest magnetic anisotropy. The development of magnetopolymeric nanofibers with adjusted length and diameter opens new opportunities in a wide range of applications.     

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 Fe(3)O(4) 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). In the present work, we just make use of the novel properties of Fe(3)O(4) MNPs as peroxidase mimetics reported by Yan et al. to detect H(2)O(2). The Fe(3)O(4) MNPs were prepared via a coprecipitation method. The as-prepared Fe(3)O(4) MNPs were then used to catalyze the oxidation of a peroxidase substrate 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) by H(2)O(2) to the oxidized colored product (see eq 1) which provides a colorimetric detection of H(2)O(2). As low as 3 x 10(-6) mol/L H(2)O(2) could be detected with a linear range from 5 x 10(-6) to 1 x 10(-4) mol/L via our method. More importantly, a sensitive and selective method for glucose detection was developed using glucose oxidase (GOx) and the as-prepared Fe(3)O(4) MNPs. The detection platforms for H(2)O(2) and glucose developed in the present work not only further confirmed that the Fe(3)O(4) MNPs possess intrinsic peroxidase-like activity but also showed great potential applications in varieties of simple, robust, and easy-to-make analytical approaches in the future.     

Fe3O4纳米粒子修饰碳纳米管的制备及其磁学性能（英文）

通过FeCl2.4H2O和FeCl3.6H2O混合共沉淀,合成平均粒径为6 nm和10 nm的Fe3O4纳米粒子。然后将两种Fe3O4纳米粒子分别与经HNO3氧化处理的多壁碳纳米管(MWCNTs)置于乙醇水溶液(水和乙醇的体积比为1∶1)中,在超声波作用下制备Fe3O4/MWCNT复合材料。用高分辨透射电子显微镜、X-射线光电子能谱、振动样品磁强计、X射线衍射仪、热重分析仪对所制备的Fe3O4/MWCNT复合材料进行表征。结果表明:由6 nm和10 nm Fe3O4纳米粒子所制备的Fe3O4/MWCNT复合材料中,Fe3O4的质量分数分别为26.65%和29.3%,相应的磁饱和强度分别为16.5 emug-1和7.5 emug-1。     

磁性羧甲基化壳聚糖纳米粒子的制备与表征

以化学共沉淀法制备了Fe3O4纳米粒子,壳聚糖经羧甲基化改性后接枝在Fe3O4颗粒表面,得到了磁性羧甲基化壳聚糖(Fe3O4/CMC)纳米粒子.利用透射电镜(TEM)、X射线衍射(XRD)、傅立叶红外光谱(FT-IR)及磁性测试对产物进行了表征.TEM表明Fe3O4纳米粒子被CMC包覆,粒径约10 nm;XRD分析表明复合纳米粒子中磁性物质为Fe3O4;FT-IR表明壳聚糖发生羧甲基反应以及在Fe3O4表面的接枝反应.Fe3O4/CMC纳米粒子具有超顺磁性,比饱和磁化强度25.73 emu/g,有良好的磁稳定性.     

Green synthesis of uniform magnetite (Fe3O4) nanoparticles and micron cubes

Single-crystalline Fe3O4 microcubes were obtained through a green hydrothermal procedure using Fe3+, Fe2+ and H2O2 as starting materials. The structures and morphologies of the as-prepared samples were characterized in detail by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) respectively. Magnetite (Fe3O4) cubes averaging 3 microm in diameter were synthesized by H2O2 oxidation of Fe3+ and Fe2+ under neutral conditions. The contrastive experiments were designed to elucidate the effects of Fe3+, Fe2+ and H2O2 on the morphology of the final products. Irregular and ellipsoidal Fe2O3 structures were obtained by H2O2 oxidation of Fe3+ and Fe2+ respectively. Meanwhile, Fe3O4 nanotubes and nanoparticles were obtained when H2O2 was replaced by NH4HCO3 and urea respectively. The results show that H2O2, Fe3+ and Fe2+ in the reactive system play critical roles in obtaining micrometric cube-like Fe3O4. While, other nanometric Fe2O3 and Fe3O4 particles with tube-like and other morphologies could also be developed by controlling the reaction parameters.     

Dumbbell-like bifunctional Au-Fe3O4 nanoparticles

Dumbbell-like Au-Fe(3)O(4) nanoparticles are synthesized using decomposition of Fe(CO)(5) on the surface of the Au nanoparticles followed by oxidation in 1-octadecene solvent. The size of the particles is tuned from 2 to 8 nm for Au and 4 nm to 20 nm for Fe(3)O(4). The particles show the characteristic surface plasmon absorption of Au and the magnetic properties of Fe(3)O(4) that are affected by the interactions between Au and Fe(3)O(4). The dumbbell is formed through epitaxial growth of iron oxide on the Au seeds, and the growth can be affected by the polarity of the solvent, as the use of diphenyl ether results in flower-like Au-Fe(3)O(4) nanoparticles.     

Mass imaging of iron oxide nanoparticles inside cells for in vitro cytotoxicity

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging analysis was performed on murine macrophage cells treated with various concentrations of iron oxide (Fe3O4) nanoparticles, which are used as MRI contrast agents. First, murine macrophage cells were seeded on a slide glass for 24 hrs and treated with varying concentrations of Fe3O4 nanoparticles for 24 hrs. To expose a cross section of each cell and obtain a distribution of the nanoparticles inside the cells, the cells were sputtered using Bi ions after which the cross section of each cell was scanned and imaged using the focused cluster ion beam with a spatial resolution of 300 nm. Fe3O4 nanoparticles were found mainly in the cytoplasm region of the cells, not in the nucleus region of cells, suggesting that the uptake of the Fe3O4 nanoparticles were into the cytoplasm of cell, not into the nucleus of cell. Based on these observations, our protocol using mass imaging analysis would be a useful addition to the study of in vitro nanoparticle cytotoxicity.     

Immobilization of functional oxide nanoparticles on silicon surfaces via Si-C bonded polymer brushes

A method for immobilizing and mediating the spatial distribution of functional oxide (such as SiO2 and Fe3O4) nanoparticles (NPs) on (100)-oriented single crystal silicon surface, via Si-C bonded poly(3-(trimethoxysilyl)propyl methacrylate) (P(TMSPM)) brushes from surface-initiated atom transfer radical polymerization (ATRP) of (3-(trimethoxysilyl)propyl methacrylate) (TMSPM), was described. The ATRP initiator was covalently immobilized via UV-induced hydrosilylation of 4-vinylbenzyl chloride (VBC) with the hydrogen-terminated Si(100) surface (Si-H surface). The surface-immobilized Fe3O4 NPs retained their superparamagnetic characteristics and their magnetization intensity could be mediated by adjusting the thickness of the P(TMSPM) brushes.     

Ni doped Fe3O4 magnetic nanoparticles

In this work, the effect of nickel doping on the structural and magnetic properties of Fe3O4 nanoparticles is analysed. Ni(x)Fe(3-x)O4 nanoparticles (x = 0, 0.04, 0.06 and 0.11) were obtained by chemical co-precipitation method, starting from a mixture of FeCl2 x 4H2O and Ni(AcO)2 x 4H2O salts. The analysis of the structure and composition of the synthesized nanoparticles confirms their nanometer size (main sizes around 10 nm) and the inclusion of the Ni atoms in the characteristic spinel structure of the magnetite Fe3O4 phase. In order to characterize in detail the structure of the samples, X-ray absorption (XANES) measurements were performed on the Ni and Fe K-edges. The results indicate the oxidation of the Ni atoms to the 2+ state and the location of the Ni2+ cations in the Fe2+ octahedral sites. With respect to the magnetic properties, the samples display the characteristic superparamagnetic behaviour, with anhysteretic magnetic response at room temperature. The estimated magnetic moment confirms the partial substitution of the Fe2+ cations by Ni2+ atoms in the octahedral sites of the spinel structure.     

交联P（St-r-AA）包覆Fe3O4粒子的制备及对Cu2＋的吸附

用乳液聚合的方法合成了交联P（St-r-AA）包覆的Fe3O4粒子,研究了该类粒子对Cu2＋离子的吸附性能。透射电镜（TEM）表明,交联的P（St-r-AA）包覆的Fe3O4磁性粒子粒径约100 nm;X射线衍射（XRD）分析表明,磁性粒子中磁性物质为尖晶石结构的Fe3O4;红外光谱（FT-IR）表明,Fe3O4表面的...     

Paraoxonase 1-bound magnetic nanoparticles: preparation and characterizations

This is most probably the first time that covalently binding of Human serum paraoxonase 1 (PON1) to superparamagnetic magnetite nanoparticles via carbodiimide activation was investigated and presented in this study. PON1 was purified from human serum using ammonium sulfate precipitation and hydrophobic interaction chromatography (Sepharose 4B, L-tyrosine, 1-Napthylamine) and magnetic iron oxide nanoparticles were prepared by co-precipitation Fe(+2) and Fe(+3) ions in an ammonia solution at room temperature. X-ray diffraction (XRD) and the magnetic measurements showed that the nanoparticles are magnetite and superparamagnetic, respectively. Direct measurements by dynamic light scattering revealed that the hydrodynamic size was 16.76 nm with polydispersity index (PDI: 0.234). The analysis of Fourier transform infrared spectroscopy revealed that the PON1 was properly bound to magnetic nanoparticles replacing the characteristic band of -NH2 at 1629 cm(-1) with the protein characteristic band at 1744 cm(-1) and 1712 cm(-1). Magnetic measurements determined that PON1-bound nanoparticles have also favorable superparamagnetic properties with zero coercivity and remanence though a slightly smaller saturation magnetization due to the decrease of magnetic moment in the volume friction. The kinetic measurements indicated the PON1-bound nanoparticles retained 70% of its original activity and exhibited an improved stability than did the free enzyme. The PON1 enzyme is seen to be quite convenient to bind superparamagnetic nanoparticles as support material.     

Synthesis of Fe3O4 nanoparticles with tunable and uniform size through simple thermal decomposition

A novel and facile method with low cost has been developed to fabricate Fe3O4 nanoparticles (NPs) with tunable and uniform sizes by the thermal decomposition of iron oleate complex. The synthesis of iron oleate complex was carried out using a reaction between oleic acid and FeCl3 x 6H2O at low temperature. The decomposition of iron oleate complex occurs when the complex added in the solution of octadecene (ODE) and trioctylamine (TOA) with simple heat treatment. The X-ray diffraction pattern of a resulting sample indicated that Fe3O4 NPs formed during the decomposition of iron oleate complex. Preparation conditions including reaction time and temperature, the concentration of the complex, and the ratio of TOA and ODE strikingly affected the size and size distribution of resulting Fe3O4 NPs. Under optimal preparation conditions, the size of Fe3O4 NPs was adjusted (less than 20 nm in average diameter). The analysis of samples by a Fourier transform infrared spectroscopy confirmed the formation of iron oleate complex. Because the Fe3O4 NPs revealed a superparamagnetic property as well as tunable and uniform sizes, the NPs will be utilizable for further applications. This simple strategy with low cost has to give a useful enlightenment for the design and fabrication of magnetic oxide.