Three-layer composite magnetic nanoparticle probes for DNA

A method for synthesizing composite nanoparticles with a gold shell, an Fe3O4 inner shell, and a silica core has been developed. The approach utilizes positively charged amino-modified SiO2 particles as templates for the assembly of negatively charged 15 nm superparamagnetic water-soluble Fe3O4 nanoparticles. The SiO2-Fe3O4 particles electrostatically attract 1-3 nm Au nanoparticle seeds that act in a subsequent step as nucleation sites for the formation of a continuous gold shell around the SiO2-Fe3O4 particles upon HAuCl4 reduction. The three-layer magnetic nanoparticles, when functionalized with oligonucleotides, exhibit the surface chemistry, optical properties, and cooperative DNA binding properties of gold nanoparticle probes, but the magnetic properties of the Fe3O4 inner shell.     

Synthesis of Fe(3)O(4)/PdO heterodimer nanocrystals in silica nanospheres and their controllable transformation into Fe(3)O(4)/Pd heterodimers and FePd nanocrystals

The thermal annealing of silica nanospheres encapsulating Fe(3)O(4) nanocrystals and Pd(2+) complexes led to the formation of heterodimers consisting of Fe(3)O(4) and PdO nanoparticles encapsulated in a silica shell, allowing for their controllable transformation into either Fe(3)O(4)/Pd heterodimers or FePd alloy nanocrystals through a solid state reduction process.     

Synthesis of Fe_3O_4@SiO_2@polymer nanoparticles for controlled drug release

Novel multifunctional nanoparticles containing a magnetic Fe3O4@SiO2 sphere and a biocompatible block copolymer poly(ethylene glycol)-b-poly(aspartate)(PEG-b-PAsp) were prepared.The silica coated on the superparamagnetic core was able to achieve a magnetic dispersivity,as well as to protect Fe3O4 against oxidation and acid corrosion.The PAsp block was grafted to the surface of Fe3O4@SiO2 nanoparticles by amido bonds,and the PEG block formed the outermost shell.The anticancer agent doxorubicin(DOX) was loade...     

Fe3O4/MIL‐101(Fe) nanocomposite as an efficient and recyclable catalyst for Strecker reaction

A highly porous metal‐organic framework, MIL‐101(Fe), was prepared by a solvothermal method in the presence of amino‐modified Fe₃O₄@SiO₂ nanoparticles, in order to achieve Fe₃O₄/MIL‐101(Fe) nanocomposite, which was characterized by XRD, FT‐IR, SEM, TEM, BET, and VSM. This hybrid magnetic nanocomposite was employed as heterogeneous catalyst for α‐amino nitriles synthesis through three‐component condensation reaction of aldehydes (ketones), amines, and trimethylsilyl cyanide in EtOH, at room temperature. The recoverability and reusability was admitted for the heterogeneous magnetic catalyst; no significant reduction of catalytic activity was observed even after five consecutive reaction cycles.     

Synthesis and characterization of multifunctional Fe3O4/poly(fluorescein O-methacrylate) core/shell nanoparticles

Multifunctional fluorescent and superparamagnetic Fe(3)O(4)/poly(fluorescein O-methacrylate) [Fe(3)O(4)/poly(FMA)] nanoparticles with core/shell structure were synthesized via surface-initiated polymerization. First, polymerizable double bonds were introduced onto the surface of Fe(3)O(4) nanoparticles via ligand exchange and a condensation reaction. A fluorescent monomer, FMA, was then polymerized to the double bonds at the surface via free-radical polymerization, leading to form a fluorescent polymer shell around the superparamagnetic Fe(3)O(4) core. The resultant Fe(3)O(4)/poly(FMA) nanoparticles were characterized by Fourier transform infrared, nuclear magnetic resonance, and X-ray diffraction spectroscopy to confirm the reactions. Transmission electron microscopy images showed that the Fe(3)O(4)/poly(FMA) nanoparticles have a spherical and monodisperse core/shell morphology. Photoluminescence spectroscopy and superconducting quantum interference device magnetometer analyses confirmed that the Fe(3)O(4)/poly(FMA) nanoparticles exhibited fluorescent and superparamagnetic properties, respectively. In addition, we demonstrated the potential bioimaging application of the Fe(3)O(4)/poly(FMA) nanoparticles by visualizing the cellular uptake of the nanoparticles into A549 lung cancer cells.     

Bifunctional nanoparticles with fluorescence and magnetism via surface-initiated AGET ATRP mediated by an iron catalyst

Fluorescent/magnetic nanoparticles are of interest in many applications in biotechnology and nanomedicine for its living detection. In this study, a novel method of surface modification of nanoparticles was first used to modify a fluorescent monomer on the surfaces of magnetic nanoparticles directly. This was achieved via iron(III)-mediated atom-transfer radical polymerization with activators generated by electron transfer (AGET ATRP). Fluorescent monomer 9-(4-vinylbenzyl)-9H-carbazole (VBK) was synthesized and was grafted from magnetic nanoparticles (ferroferric oxide) via AGET ATRP using FeCl(3)·6H(2)O as the catalyst, tris(3,6-dioxaheptyl)amine (TDA-1) as the ligand, and ascorbic acid (AsAc) as the reducing agent. The initiator for ATRP was modified on magnetic nanoparticles with the reported method: ligand exchange with 3-aminopropyltriethoxysilane (APTES) and then esterification with 2-bromoisobutyryl bromide. After polymerization, a well-defined nanocomposite (Fe(3)O(4)@PVBK) was yielded with a magnetic core and a fluorescent shell (PVBK). Subsequently, well-dispersed bifunctional nanoparticles (Fe(3)O(4)@PVBK-b-P(PEGMA)) in water were obtained via consecutive AGET ATRP of hydrophilic monomer poly(ethylene glycol) methyl ether methacrylate (PEGMA). The chemical composition of the magnetic nanoparticles' surface at different surface modification stages was investigated with Fourier transform infrared (FT-IR) spectra. The magnetic and fluorescent properties were validated with a vibrating sample magnetometer (VSM) and a fluorophotometer. The Fe(3)O(4)@PVBK-b-P(PEGMA) nanoparticles showed an effective imaging ability in enhancing the negative contrast in magnetic resonance imaging (MRI).     

Fe3 O4@(TF-LDHs)纳米复合体的制备及药物缓释性能

采用共沉淀法, 以替加氟(Tegafur, TF)插层层状双金属氢氧化物(LDHs)纳米杂化物(TF-LDHs)包覆磁性基质Fe3O4, 得到了具有核/壳结构的纳米复合体[Fe3O4@(TF-LDHs)], 采用XRD, FTIR, TEM, VSM和元素分析等技术对样品的化学组成、 晶体结构\, 形貌及磁性等进行了表征, 探讨了药物分子在LDHs层间的存在状态, 考察了其药物释放行为. 结果表明, Fe3O4@(TF-LDHs)纳米复合体具有顺磁性, 其比饱和磁化强度随磁性基质含量的增大而增强; TF分子在LDHs层间以长轴略倾斜于LDHs层板的方式呈双层排布; Fe3O4@(TF-LDHs)纳米复合体具有明显的药物缓释性能, 其释放动力学过程符合准二级动力学方程, 颗粒内部扩散为释放过程的速率控制步骤.     

Controlled synthesis of magnetic Pd/Fe3O4 spheres via an ethylenediamine-assisted route

A simple route based on time-dependent growth was employed to synthesize solid and hollow spheres of Pd/Fe(3)O(4) nanocomposite. Transmission electron microscopic (TEM) imaging shows that the spheres are composed of nanocrystals with the solid spheres having a diameter of 533 nm whereas the hollow ones having a diameter of 520 nm and a shell thickness of 100 nm. An assembly-then-growth mechanism for the formation of the magnetic Pd/Fe(3)O(4) nanocomposite has also been elucidated on the basis of the experimental observations. It is demonstrated that the Pd/Fe(3)O(4) nanocomposite functions as a heterogeneous catalyst for the hydrogenation reaction of p-nitrophenol at room temperature under atmospheric pressure. Both the solid and hollow spheres possess unique magnetic properties so that they may be conveniently separated and recovered by a magnet after the catalytic reaction.     

磁性聚苯胺纳米微球的合成与表征

报道了具有核壳结构的Fe3O4-聚苯胺磁性纳米微球的合成方法和表征结果.微球同时具有导电性和磁性能.在优化的实验条件下,可得到饱和磁化强度Ms为55.4 emu/g,矫顽力Hc为62 Oe的磁性微球.微球的导电性随着微球中Fe含量的增加而下降.微球的磁性能则随着Fe含量的增加而增大.Fe3O4磁流体的粒径和磁性聚苯胺微球的粒径均在纳米量级.纳米Fe3O4粒子能够提高复合物的热性能.实验表明,磁流体和聚苯胺之间可能存在着一定的相互作用,但这种相互作用较为复杂,难于研究     

Preparation of Silica/Poly(tert‐butylmethacrylate) Core/Shell Nanocomposite Latex Particles

Nanocomposite latex particles, with a silica nanoparticle as core and crosslinked poly(tert‐butylmethacrylate) as shell, were prepared in this work. Silica nanoparticles were first synthesized by a sol‐gel process, and then modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) to graft C?C groups on their surfaces. The MPS‐modified silica nanoparticles were characterized by elemental analysis, FTIR, and ²⁹Si NMR and ¹³C‐NMR spectroscopy; the results showed that the C?C groups were successfully grafted on the surface of the silica nanoparticles and the grafted substance was mostly the oligomer formed by the hydrolysis and condensation reaction of MPS. Silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were prepared via seed emulsion polymerization using the MPS‐modified silica nanoparticle as seed, tert‐butylmethacrylate as monomer and ethyleneglycol dimethacrylate as crosslinker. Their core/shell nanocomposite structure and chemical composition were characterized by means of TEM and FTIR, respectively, and the results indicated that silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were obtained.     

Synthesis of a novel magnetic drug delivery system composed of doxorubicin-conjugated Fe3O4 nanoparticle cores and a PEG-functionalized porous silica shell

Coating a layer of PEG functionalized porous silica shell onto doxorubicin-conjugated Fe(3)O(4) nanoparticles, we demonstrated, provides a number of combined advantages in view of the magnetic carrier's therapeutic functionality to treat tumors.     

Control of shell thickness in silica-coating of Au nanoparticles and their X-ray imaging properties

This paper describes a performance of precise control of shell thickness in silica-coating of Au nanoparticles based on a sol-gel process, and an investigation into X-ray imaging properties for the silica-coated Au (Au/SiO(2)) particles. The Au nanoparticles with a size of 16.9±1.2 nm prepared through a conventional citrate reduction method were used as core particles. The Au nanoparticles were silica-coated with a sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica source, sodium hydroxide (NaOH) as a catalyst, and (3-aminopropyl) trimethoxysilane (APMS) as a silane coupling agent. An increase in TEOS concentration resulted in an increase in shell thickness. Under certain concentrations of Au, H(2)O, NaOH, and APMS, the Au/SiO(2) particles with silica shell thickness of 6.0-61.0 nm were produced with varying TEOS concentration. Absorption peak wavelength of surface plasmon resonance of the Au/SiO(2) colloid solution depended on silica shell thickness, which agreed approximately with the predictions by Mie theory. The as-prepared colloid solution could be concentrated up to an Au concentration of 0.19 M with salting-out and centrifugation. The concentrated colloid solution showed an X-ray image with high contrast, and a computed tomography value for the colloid solution with an Au concentration of 0.129 M was achieved 1329.7±52.7 HU.     

Porous Fe3O4 nanoparticles: synthesis and application in catalyzing epoxidation of styrene

A facile route was employed to synthesize porous magnetite via reaction of FeCl(3)·6H(2)O with N(2)H(4)·H(2)O in ethylene glycol without any structure-directing agent. The resultant Fe(3)O(4) particles were characterized by transmission electron microscopy, N(2) adsorption, X-ray photoelectron spectroscopy, and thermal gravimetric analysis. It was demonstrated that the particle size varied in the range of 40-220 nm, and the pore size of particles was centered around 2 nm. The gases produced in the formation process of the particles played key role in the formation of the porous structure. The obtained porous magnetite was used as support to immobilize Au nanoparticles with size less than 2 nm with the assistance of L-cysteine. The as-prepared Fe(3)O(4) particles can effectively catalyze epoxidation of styrene, and the immobilization of Au nanoparticles on the Fe(3)O(4) support significantly improved the activity of the catalyst.     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.     

In situ small-angle X-ray scattering studies during the formation of polymer/silica nanocomposite particles in aqueous solution

This study is focused on the formation of polymer/silica nanocomposite particles prepared by the surfactant-free aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) in the presence of 19 nm glycerol-functionalized aqueous silica nanoparticles using a cationic azo initiator at 60 °C. The TFEMA polymerization kinetics are monitored using ¹H NMR spectroscopy, while postmortem TEM analysis confirms that the final nanocomposite particles possess a well-defined core–shell morphology. Time-resolved small-angle X-ray scattering (SAXS) is used in conjunction with a stirrable reaction cell to monitor the evolution of the nanocomposite particle diameter, mean silica shell thickness, mean number of silica nanoparticles within the shell, silica aggregation efficiency and packing density during the TFEMA polymerization. Nucleation occurs after 10–15 min and the nascent particles quickly become swollen with TFEMA monomer, which leads to a relatively fast rate of polymerization. Additional surface area is created as these initial particles grow and anionic silica nanoparticles adsorb at the particle surface to maintain a relatively high surface coverage and hence ensure colloidal stability. At high TFEMA conversion, a contiguous silica shell is formed and essentially no further adsorption of silica nanoparticles occurs. A population balance model is introduced into the SAXS model to account for the gradual incorporation of the silica nanoparticles within the nanocomposite particles. The final PTFEMA/silica nanocomposite particles are obtained at 96% TFEMA conversion after 140 min, have a volume-average diameter of 216 ± 9 nm and contain approximately 274 silica nanoparticles within their outer shells; a silica aggregation efficiency of 75% can be achieved for such formulations.

SAXS is used to study the formation of polymer/silica nanocomposite particles prepared by surfactant-free aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate in the presence of silica nanoparticles using a azo initiator at 60 °C.     

含稀土氨合成催化剂还原的研究

氨合成铁催化剂中添加稀土氧化物已有不少报道,有的活性有所提高.我们通过添加稀土. 调整催化剂组成和改进制工艺得到几种活性较高,而且是非常容易还原的催化剂.本文的目的是研究稀土氧化物对催化剂还原性能的影响及几种活性较高容易还原的含稀土催化剂的本征还原动力学.     

In Situ Confined Growth Based on a Self‐Templating Reduction Strategy of Highly Dispersed Ni Nanoparticles in Hierarchical Yolk–Shell Fe@SiO2 Structures as Efficient Catalysts

Ni‐based magnetic catalysts exhibit moderate activity, low cost, and magnetic reusability in hydrogenation reactions. However, Ni nanoparticles anchored on magnetic supports commonly suffer from undesirable agglomeration during catalytic reactions due to the relatively weak affinity of the magnetic support for the Ni nanoparticles. A hierarchical yolk–shell Fe@SiO₂/Ni catalyst, with an inner movable Fe core and an ultrathin SiO₂/Ni shell composed of nanosheets, was synthesized in a self‐templating reduction strategy with a hierarchical yolk–shell Fe₃O₄@nickel silicate nanocomposite as the precursor. The spatial confinement of highly dispersed Ni nanoparticles with a mean size of 4 nm within ultrathin SiO₂ nanosheets with a thickness of 2.6 nm not only prevented their agglomeration during catalytic transformations but also exposed the abundant active Ni sites to reactants. Moreover, the large inner cavities and interlayer spaces between the assembled ultrathin SiO₂/Ni nanosheets provided suitable mesoporous channels for diffusion of the reactants towards the active sites. As expected, the Fe@SiO₂/Ni catalyst displayed high activity, high stability, and magnetic recoverability for the reduction of nitroaromatic compounds. In particular, the Ni‐based catalyst in the conversion of 4‐nitroamine maintained a rate of over 98 % and preserved the initial yolk–shell structure without any obvious aggregation of Ni nanoparticles after ten catalytic cycles, which confirmed the high structural stability of the Ni‐based catalyst.     

Exchange‐Coupled fct‐FePd/α‐Fe Nanocomposite Magnets Converted from Pd/Fe3O4 Core/Shell Nanoparticles

We report the controlled synthesis of exchange‐coupled face‐centered tetragonal (fct) FePd/α‐Fe nanocomposite magnets with variable Fe concentration. The composite was converted from Pd/Fe₃O₄ core/shell nanoparticles through a high‐temperature annealing process in a reducing atmosphere. The shell thickness of core/shell Pd/Fe₃O₄ nanoparticles could be readily tuned, and subsequently the concentration of Fe in nanocomposite magnets was controlled. Upon annealing reduction, the hard magnetic fct‐FePd phase was formed by the interdiffusion between reduced α‐Fe and face‐centered cubic (fcc) Pd, whereas the excessive α‐Fe remained around the fct‐FePd grains, realizing exchange coupling between the soft magnetic α‐Fe and hard magnetic fct‐FePd phases. Magnetic measurements showed variation in the magnetic properties of the nanocomposite magnets with different compositions, indicating distinct exchange coupling at the interfaces. The coercivity of the exchange‐coupled nanocomposites could be tuned from 0.7 to 2.8 kOe and the saturation magnetization could be controlled from 93 to 160 emu g^?1. This work provides a bottom‐up approach using exchange‐coupled nanocomposites for engineering advanced permanent magnets with controllable magnetic properties.     

磁微球负载氯化血红素仿酶催化剂制备及催化降解DMP

采用超声辅助反向共沉淀法制得磁纳米Fe3O4颗粒,然后以磁纳米Fe3O4颗粒为种子采用种子乳液聚合法制得羟基功能化的磁纳米复合物微球,再以三聚氯氰为桥联剂键合氯化血红素制得磁微球负载氯化血红素仿酶催化剂.利用傅里叶变换红外光谱仪（FT-IR）、配置积分球的紫外-可见（UV-Vis）分光光度计、透射电子显微镜（TEM）、热重分析仪（TGA）和振动样品磁强计（VSM）对催化剂进行了表征.结果表明,催化剂粒径大小为10～12 nm,粒度均一,分散性好,在300 K下具有一定顺磁性,饱和磁化强度为21.61 emu/g,磁性物质含量为52.50%.催化剂在紫外光照和H2O2存在下对水中邻苯二甲酸二甲酯（DMP）有较高的氧化降解活性,且重复使用效果较好.     

Synthesis of thiazole derivatives using magnetic nano zirconia–sulfuric acid as an efficient and recyclable catalyst in water

Russian Journal of General Chemistry - Fe3O4 magnetic core covered by zirconia shell bearing sulfonic acid groups (Fe3O4@ZrO2–SO3H) was prepared and used as an efficient acidic catalyst in...