One-pot synthesis of dual-stimuli responsive hybrid PNIPAAm-chitosan microgels

The incorporation of magnetic nanoparticles into poly(N-isopropylacrylamide) (PNIPAAm) and chitosan microgels gives rise to hybrid systems that combine the microgels swelling capacity with the interesting features presented in magnetic nanoparticles. The presence of chitosan that act as surfactant for magnetic nanoparticles provides a simplistic approach which allows the encapsulation of magnetic nanoparticles without any previous surface modification. Spherical and highly monodisperse microgels with diameters in the range of 200 to 500 nm were obtained. The encapsulation of magnetic nanoparticles in the polymer matrix was confirmed by high resolution Scanning Electron Microscopy in transmission mode. Volume phase transition of the microgels was accessed by Dynamic Light Scattering measurements. It was observed that the thermosensitivity of the PNIPAM microgels still persists in the hybrid microgels; however, the swelling ability is compromised in the microgels with highest chitosan content. The heating performance of the hybrid magnetic microgels, when submitted to an alternating magnetic field, was also evaluated demonstrating the potential of these systems for hyperthermia treatments.     

Preparation and characterization of thermo-, pH-, and magnetic-field-responsive organic/inorganic hybrid microgels based on poly(ethylene glycol)

Nanocomposite microgels are a new class of intelligent materials because of their fast response time, large surface area, and so on. In this study, we demonstrate a new kind of multiple stimulus-responsive organic/inorganic hybrid microgels by combining dual stimuli-responsive poly(2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol)methacrylate-co-acrylic acid) (PMOA) microgels with magnetic attapulgite/Fe₃O₄ (AT–Fe₃O₄) nanoparticles. AT–Fe₃O₄ nanoparticles were introduced into the dual-responsive (temperature and pH) PMOA microgels network by in situ polymerization. The responsive behaviors, microstructures, and the interaction between AT–Fe₃O₄ and PMOA microgels matrix of the prepared microgels were systematically characterized using field emission scanning electron microscopy, particle size and Zeta potential analyzer, vibrating sample magnetometer, and Fourier transform infrared spectroscopy. The results showed that the AT–Fe₃O₄ nanoparticles dispersed well in the microgel matrix, and the nanoparticles could be stably present in PMOA without phase separation because of the hydrogen bond (H-bond) interactions between AT–Fe₃O₄ nanoparticles and PMOA matrix. In addition, the multifunctional AT–Fe₃O₄/PMOA nanocomposite microgels had both temperature/pH sensitivity and magnetic functionality.     

Design of multicomponent microgels by selective deposition of nanomaterials

In the present paper a method for the targeted deposition of different nanomaterials on aqueous microgels is described. In the first stage poly(3,4-ethylenedioxythiophene) (PEDOT) nanorods are introduced into the microgel structure by in situ oxidative polymerization. In the second stage hydrogen tetrachloroaurate is used to transform PEDOT chains to an oxidized state in the microgel structure, leading to the fixation of chloroaurate anions on the surface of the PEDOT nanorods. The reduction of chloroaurate ions induces the formation of gold nanoparticles (AuNPs) predominantly located on the PEDOT surface. Obtained microgel/PEDOT/AuNP hybrid particles with different nanoparticle loadings exhibit superior colloidal stability and temperature sensitivity. The microgel/PEDOT/AuNP hybrid microgels exhibit extraordinary catalytic activity in aqueous media.     

Fabrication of DNA-magnetite hybrid nanofibers for water detoxification

DNA-magnetite hybrid nanofibers were fabricated by electrospinning a spin dope consisting of oleic acid coated magnetite nanoparticles and DNA-CTMA in ethanol/chloroform mixed solvent. The fabricated nanofibers exhibit superparamagnetic behaviour owing to embedded magnetite nanoparticles. It is demonstrated that these nanofibers can be used as effective detoxification materials in aqueous media as a combined result of DNA's affinity to both organic and inorganic toxicants, high surface area of the nanofibers and the fast and easy separation due to magnetite nanoparticles under external magnetic field. In addition to detoxification, these novel hybrid nanofibers have potential applications in many technological areas such as catalysis and drug delivery.     

Synthesis of Fe3O4@PbS hybrid nanoparticles through the combination of surface-initiated atom transfer radical polymerization and acidolysis by H2S

A versatile approach to fabricate nanoparticles with multiple functionalities through the combined use of both surface-initiated ATRP and acidolysis by H2S techniques was demonstrated. The hybrid nanoparticles exhibited the core-shell structure having the magnetite nanoparticles as the core and the polymethacrylate as the shell with PbS nanoparticles distributing in the shell. The structure and morphology of the synthesized nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical and magnetic properties of the nanoparticles were investigated by UV-Vis spectroscopy, photoluminescence spectroscopy and vibrating sample magnetometer (VSM), respectively. It is observed that the absorption and emission behaviors of the Fe3O4@PbS hybrid nanoparticles were seriously influenced by the ATRP time and the reaction time with H2S. The saturated magnetization (Ms) decreased with the increase of ATRP time due to the formation of thicker shells coating on the surfaces of magnetite nanoparticles.     

Tuneable catalytic properties of hybrid microgels containing gold nanoparticles

A novel type of submicrometer-sized hybrid microgels containing gold nano-particles (AuNPs) has been tested as catalyst in reduction of 4-nitrophenol in aqueous medium. The influence of microgel concentration, gold content, as well as temperature of reaction medium on kinetics of 4-nitrophenol reduction process has been investigated. The pseudo-first-order kinetics was used to evaluate the catalytic reaction rate. It has been demonstrated that reaction rate of 4-nitrophenol reduction can be accelerated if the concentration of microgel in the reaction system or amount of gold nanoparticles loaded into microgels increases. Increase of reaction temperature resulted in rapid increase of reduction rate. Compared to pure gold nano-particles hybrid microgels at similar conditions reduce the activation energy of reduction process by a factor of 2. This indicates that localization of AuNPs within microgel template prevents their aggregation and therefore high catalytic activity can be preserved independently from reaction conditions. Additionally, polymeric template provides suitable environment for better mass transfer in present system that improves the catalyst efficiency.     

Simple synthesis of functionalized superparamagnetic magnetite/silica core/shell nanoparticles and their application as magnetically separable high-performance biocatalysts

Uniformly sized silica-coated magnetic nanoparticles (magnetite@silica) are synthesized in a simple one-pot process using reverse micelles as nanoreactors. The core diameter of the magnetic nanoparticles is easily controlled by adjusting the w value ([polar solvent]/[surfactant]) in the reverse-micelle solution, and the thickness of the silica shell is easily controlled by varying the amount of tetraethyl orthosilicate added after the synthesis of the magnetite cores. Several grams of monodisperse magnetite@silica nanoparticles can be synthesized without going through any size-selection process. When crosslinked enzyme molecules form clusters on the surfaces of the magnetite@silica nanoparticles, the resulting hybrid composites are magnetically separable, highly active, and stable under harsh shaking conditions for more than 15 days. Conversely, covalently attached enzymes on the surface of the magnetite@silica nanoparticles are deactivated under the same conditions.     

Oriented growth of magnetite along the carbon nanotubes via covalently bonded method in a simple solvothermal system

A new type of CNTs/magnetite hybrid material was prepared via covalently bonded method in a simple solvothermal system using FeCl₃ as iron source, ethylene glycol as the reducing agent, and 4-aminophenoxyphthalonitrile-grafted CNTs as templates. The magnetite nanoparticles, with the diameters of 70-80 nm, were self-assembled along the CNTs. The FTIR, UV-vis and DSC revealed that a stable covalent bond between nitriles group and iron ion promoted the oriented growth of magnetite nanoparticles along the CNTs, resulting in good dispersibility and solution storage stability. The magnetic properties measurements indicated that a higher saturated magnetization (70.7 emu g⁻¹) existed in the CNTs/magnetite hybrid material, which further enhanced the electromagnetic properties. The magnetic loss was caused mainly by natural resonance, which is in good agreement with the Kittel equation results. The novel electromagnetic hybrid material is believed to have potential applications in the microwave absorbing performances.     

Sustained release of doxorubicin from zeolite-magnetite nanocomposites prepared by mechanical activation

Nanocomposites consisting of magnetite and FAU zeolite with a high surface area and adsorption capacity have been prepared by mechanical activation using high-energy milling at room temperature. FTIR results, as well as HRTEM, EFTEM, and XPS measurements, show that the resulting magnetic nanoparticles are covered by a thin aluminosilicate coating. A saturation magnetization as high as 16?emu?g(-1) and 94.2?Oe of coercivity were observed for the obtained composites. The main advantages of this synthesis procedure are (i) simplicity of the preparation procedure, (ii) prevention of agglomeration of the magnetite nanoparticles to a large extent, and (iii)?absence of free magnetite outside the zeolitic matrix. In addition, in vitro experiments revealed that the nanoparticles prepared were able to store and release substantial amounts of doxorubicin. In view of these advantages, these magnetic nanoparticles can be considered as potential candidates for drug-delivery applications.     

核-壳结构纳米磁性复合颗粒的化学制备及应用进展

核-壳结构纳米磁性颗粒作为一种新型材料,具有广泛的应用前景,克服了磁性粒子易于团聚、化学稳定性不高、易受氧化、表面羟基不足等缺点。文中综述了Fe3O4/聚合物和Fe3O4/SiO2两大类核-壳结构的纳米磁性复合颗粒的化学制备方法,包括溶胶-凝胶法、硅烷化反应法、聚合法、自组装法、超声波法、高温合成法、凝结法、超临界流体...     

Preparation and characterization of iminodiacetic acid-functionalized magnetic nanoparticles and its selective removal of bovine hemoglobin

In this study, a novel route for the preparation of magnetite (Fe(3)O(4)) nanoparticles (NPs) with immobilized metal affinity ligand iminodiacetic acid (IDA) charged with Cu(2+) was developed. First, magnetite nanoparticles were synthesized by a hydrothermal method. Charged with Cu(2+), the magnetic nanoparticles (MNPs) were applied to separate a model protein mixture of bovine hemoglobin (BHb) and bovine serum albumin (BSA). They could be separated completely and showed low non-specific adsorption. The morphology, structure and composition of the magnetite MNPs were characterized by transmission electron microscopy, power x-ray diffraction, x-ray photoelectron spectrometry and Fourier transform infrared spectroscopy. The resulting magnetite MNPs charged with Cu(2+) show not only a strong magnetic response to externally applied magnetic field, but are also highly specific to protein BHb. It is interesting that MNPs modified with metal ligands showed a property of magnetic colloid photonic crystals. Furthermore, they could efficiently remove the abundant protein bovine hemoglobin from bovine blood. They have potential application in removing abundant protein in proteomic analysis.     

Temperature-responsive hybrid microgels for catalytic applications: a review

Temperature-responsive hybrid microgels have been extensively used as catalyst for degradation of toxic chemicals in the last 10 years. Various architectures of such kind of hybrid microgels with tunable catalytic activity have been reported in literature. Recent research progress in synthesis, characterisation and catalytic applications of various hybrid microgels based on N-isopropylacrylamide has been described critically in this article. Mechanism of catalysis and factors affecting the rate of catalysis by hybrid microgels have been discussed in the light of research done in this area. Possible future studies for further development in this area have been also predicted in this article.     

温度感应型凝胶微粒研究进展

简要综述了感温型凝胶微粒的微观结构，及其制备方法和影响其膨胀—收缩性能的主要因素等方面的研究进展。迄今凝胶微粒按微观结构可分为均质型和核—壳型两大类。制备均质结构凝胶微粒常采用无皂轧液聚合；制备核—壳结构时，常先采用无皂轧液合成核颗粒，再在核表面通过包缚或接枝分别形成交联式或线形凝胶壳层。为了使凝胶微粒有较大的体积膨胀率和温度感应速度，常在制备壳层时在单体溶液中加入一些离子基团。凝胶微粒的温度感应特性会随化学环境的变化而不同。     

Bi-layered polymer–magnetite core/shell particles: synthesis and characterization

Polymer magnetic core particles receive growing attention due to these materials owing magnetic properties which are widely used in different applications. The prepared composite particles are characterized with different properties namely: a magnetic core, a hydrophobic first shell, and finally an external second hydrophilic shell. The present study describes a method for the preparation of bi-layered polymer magnetic core particles (diameter range is 50–150 nm). This method comprises several steps including the precipitation of the magnetic iron oxide, coating the magnetite with oleic acid, attaching the first polymer shell by miniemulsion polymerization and finally introducing hydrophilic surface properties by condensation polymerization. The first step is the formation of magnetite nanoparticles within a co-precipitation process using oleic acid as the stabilizing agent for magnetite. The second step is the encapsulation of magnetite into polyvinylbenzyl chloride particles by miniemulsion polymerization to form a magnetic core with a hydrophobic polymer shell. The hydrophobic shell is desired to protect magnetite nanoparticles against chemical attack. The third step is the coating of magnetic core hydrophobic polymer shell composites with a hydrophilic layer of polyethylene glycol by condensation polymerization. Regarding the miniemulsion polymerization the influence of the amount of water, the mixing intensity and the surfactant concentration were studied with respect to the formation of particles which can be further used in chemical engineering applications. The resulting magnetic polymer nanoparticles were characterized by particle size measurement, chemical stability, iron content, TEM, SEM, and IR.     

Synthesis of magnetite nanoparticles by surfactant-free electrochemical method in an aqueous system

A simple surfactant-free electrochemical method is proposed for the preparation of magnetite nanoparticles using iron as the anode and plain water as the electrolyte. This study observed the effects of certain parameters on the formation of magnetite nanoparticles and their mechanism in the system, including the role of OH^? ions, the distance between electrodes and current density. We found that OH^? ions play an important role in the formation of magnetite nanoparticles. Particle size can be controlled by adjusting the current density and the distance between electrodes. Particle size increases by increasing the current density and by decreasing the distance between electrodes. Particle formation cannot be favored when the distance between electrodes is larger than a critical value. The magnetite nanoparticles produced by this method are nearly spherical with a mean size ranging from 10 to 30 nm depending on the experimental conditions. They exhibit ferromagnetic properties with a coercivity ranging from 140 to 295 Oe and a saturation magnetization ranging from 60 to 70 emu g^?1, which is lower than that of the corresponding bulk Fe₃O₄ (92 emu g^?1). This simple method appears to be promising as a synthetic route to producing magnetite nanoparticles.     

超顺磁单分散性Fe3O4磁纳米粒的制备及性能表征

具有超顺磁单分散性的Fe₃O₄磁纳米粒在生物医学材料领域有着广泛的用途. 本研究在水、乙醇和甲苯混合体系74℃回流的条件下制备了具有超顺磁性的表面含油酸的Fe₃O₄磁纳米粒,研究了制备过程中OH^-浓度的变化对磁纳米粒的表面性能、粒径、分散性及磁性能的影响, 并对其机理进行了初步探讨. 采用XRD、FTIR、DLS、TEM和VSM等手段对制备的磁纳米粒进行表征. 结果表明, 当NaOH/Fe(Ⅱ)摩尔比＜8时, Fe₃O₄磁纳米粒表面含油酸可良好地分散于非极性溶剂中, NaOH的加入对磁纳米粒的粒径和饱和磁化强度等性能无明显影响;而当NaOH/Fe(Ⅱ)摩尔比≥8时, Fe₃O₄磁纳米粒仅能分散于水等极性溶剂中, 饱和磁化强度虽可增至40A·m²/kg, 但为多分散且易团聚.     

Removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles

Diatomite-supported/unsupported magnetite nanoparticles were prepared by co-precipitation and hydrosol methods, and characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the unsupported and supported magnetite nanoparticles are around 25 and 15 nm, respectively. The supported magnetite nanoparticles exist on the surface or inside the pores of diatom shells, with better dispersing and less coaggregation than the unsupported ones. The uptake of hexavalent chromium [Cr(VI)] on the synthesized magnetite nanoparticles was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium [Cr(III)]. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed a pseudo-second-order model. The adsorption data of diatomite-supported/unsupported magnetite fit well with the Langmuir isotherm equation. The supported magnetite showed a better adsorption capacity per unit mass of magnetite than unsupported magnetite, and was more thermally stable than their unsupported counterparts. These results indicate that the diatomite-supported/unsupported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.     

磁性纳米Fe3O4的制备与应用进展

总结了磁性纳米Fe3O4粒子的微乳液法、热分解铁有机物法、共沉淀法、凝胶-溶胶法、生物模板合成法等.并讨论了磁性纳米Fe3O4粒子在生物分离、靶向药物、肿瘤磁热疗以及免疫检测等领域的应用.     

Gold nanoparticles bound on microgel particles and their application as an enzyme support

Submicron-sized poly(N-isopropyl acrylamide)/polyethyleneimine core-shell microgels were prepared in aqueous media by using tert-butyl hydroperoxide (TBHP) as an initiator, and then the gold nanoparticles (～8?nm) were formed on the surface of the microgels. The amino groups on the polyethyleneimine (PEI) chains act as the binder for the assembly of the gold nanoparticles/microgel complex. In aqueous media the microgels are highly stable with the gold nanoparticles on their extended PEI chains, and this multi-scale nanoparticle complex can be recovered from water and redispersed in water. The nanogold/microgel particles were conjugated with the enzymes horseradish peroxidase (HRP) and urease. It is found that under identical assay conditions the enzyme/nanogold/microgel systems exhibit enhanced biocatalytic activity over free enzymes in solution, especially at lower enzyme concentrations. In addition, compared to free HRP, the HRP/nanogold/microgel systems show higher activity at varied pHs and temperatures, as well as higher storage stability. Thus the novel nanogold/microgel particles can serve as an excellent support for enzymes.     

Tuning of magnetite nanoparticles to hyperthermic thermoseed by controlled spray method

Magnetite nanoparticles with super-paramagnetic properties have great potential to achieve advances in fields such as hyperthermia, magnetic resonance imaging and magnetic drug targeting. In particular, magnetic particles less than 50 nm are easily incorporated into cells and generate heat under an alternating magnetic field by hysteresis loss. Various methods of preparing magnetic particles have attracted attention, such as spray pyrolysis, microwave irradiation of ferrous hydroxide, microemulsion technique and hydrothermial preparation technique. In this study, magnetite nanoparticles were synthesized with various molar ratio of Fe²⁺ and Fe³⁺ by coprecipitation using spray-guns and dropping syringe. Experiments at different molar concentrations of Fe ions were conducted, which shows the ideal molar concentration of Fe²⁺ to be 0.5 M for pure magnetite. Both in the spray and drop method, pure magnetite nanoparticles could be synthesized when the molar concentration of Fe²⁺ was 0.5 M. With increasing the molar ratio of Fe²⁺, the particle size of the magnetite nanoparticles was increased. The smallest size could be reduced to approximately 7 nm by the spray method. The shape of the synthesized nanoparticles was nearly spherical. The calculated highest loss power by hysteresis losses was 597 W/g, generated with a molar concentration ratio of 0.5:1 (Fe²⁺:Fe³⁺).