Directed self-assembly of two kinds of nanoparticles utilizing monolayer films of diblock copolymer micelles

We demonstrated a self-assembly of two different kinds of nanoparticles simultaneously directed on a monolayer film of diblock copolymer micelles via physical and chemical arrangements. We first incorporated gold nanoparticles physically around the micelles of a monolayer film of PS-PVP micelles having a short-range hexagonal order. Iron oxide nanoparticles were then synthesized chemically in the PVP core area of the ordered micelles, resulting in a mosaic nanopattern of magnetic iron oxide nanoparticles surrounded by metallic gold nanoparticles. Thus, we were able to direct two kinds of nanoparticles to self-assemble in the specific positions as an example of controlled fabrication of nanometer-sized building blocks.     

Mixed Co/Fe oxide nanoparticles in block copolymer micelles

Small iron oxide and Co-doped iron oxide nanoparticles (NPs) were synthesized in a commercial amphiphilic block copolymer, poly(ethylene oxide)-b-poly(methacrylic acid) (PEO 68-b-PMAA8), in aqueous solutions. The structure and composition of the micelles containing guest molecules (metal salts) or NPs (metal oxides) were studied using transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The enlarged micelle cores after incorporation of metal salts are believed to be formed by both PMAA blocks containing metal species and penetrating PEO chains. The nanoparticle size distributions in PEO 68-b-PMAA8 were determined using small-angle X-ray scattering (SAXS) in bulk. Two independent methods for SAXS data interpretation for comprehensive analysis of volume distributions of metal oxide NPs showed presence of both small particles and larger entities containing metal species which are ascribed to organization of block copolymer micelles in bulk. The magnetometry measurements revealed that the NPs are superparamagnetic and their characteristics depend on the method of the NP synthesis. The important advantage of the PEO 68-b-PMAA8 stabilized magnetic nanoparticles described in this paper is their remarkable solubility and stability in water and buffers.     

Uniformly sized gold nanoparticles derived from PS-b-P2VP block copolymer templates for the controllable synthesis of Si nanowires

A monolayer of gold-containing surface micelles has been produced by spin-coating solution micelles formed by the self-assembly of the gold-modified polystyrene-b-poly(2-vinylpyridine) block copolymer in toluene. After oxygen plasma removed the block copolymer template, highly ordered and uniformly sized nanoparticles have been generated. Unlike other published methods that require reduction treatments to form gold nanoparticles in the zero-valent state, these as-synthesized nanoparticles are in form of metallic gold. These gold nanoparticles have been demonstrated to be an excellent catalyst system for growing small-diameter silicon nanowires. The uniformly sized gold nanoparticles have promoted the controllable synthesis of silicon nanowires with a narrow diameter distribution. Because of the ability to form a monolayer of surface micelles with a high degree of order, evenly distributed gold nanoparticles have been produced on a surface. As a result, uniformly distributed, high-density silicon nanowires have been generated. The process described herein is fully compatible with existing semiconductor processing techniques and can be readily integrated into device fabrication.     

A Coupled Chemical Kinetic and Nucleation Model of Fume Formation in Metal–Inert-Gas/Metal–Active-Gas Welding

A computational model of the formation of welding fume in arc plasmas, under conditions occurring in metal–inert-gas (MIG) and metal–active-gas (MAG) welding, is presented. The model couples the chemical kinetics occurring in high-temperature mixtures of iron vapour, oxygen and argon with a moment model of the nucleation and growth by condensation of iron and iron oxide nanoparticles. Results are presented for different iron vapour concentrations, oxygen-to-argon ratios, and quench rates. It is found that the presence of oxygen has important effects on the gas-phase chemistry and the properties of the nanoparticles. FeO nanoparticles are preferentially nucleated, and have smaller diameter than the Fe nanoparticles that are produced in the absence of oxygen. The final composition of the nanoparticles depends on the relative concentrations of iron and oxygen in the plasma. A three-dimensional arc model that includes vaporization of the wire electrode is used to predict temperature, velocity and iron vapour mass fraction distributions in typical MIG and MAG welding conditions. Calculations of nanoparticle formation and growth along streamlines confirm the importance of oxygen in determining the fume particle properties.     

Effect of hydrophobicity inside PEO-PPO-PEO block copolymer micelles on the stabilization of gold nanoparticles: experiments

In this paper we present the effect of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer micelles and their hydrophobicity on the stabilization of gold nanoparticles. Gold nanoparticles were prepared by a method developed by Sakai et al. (Sakai, T.; Alexandridis, P. Langmuir 2004, 20, 8426). An absorption centered at 300-400 nm in time-dependent UV spectra provided evidence that the very first step of the synthesis was to form primary gold clusters. Then the gold clusters grew in size and were stabilized by block copolymer micelles. The stabilization capacities of the micelles were modulated by tuning the block copolymer concentration and composition and by adding salts. With good stabilization, gold particles were spherical and uniform in size with a diameter of 5-10 nm. Otherwise they were aggregates with irregular shapes such as triangular, hexagonal, and rodlike. The presence of a small amount of NaF significantly increased the stabilization capacity of the micelles and consequently modified the quality of the gold particles. Using FTIR and 1H NMR spectroscopy, micellization of the block copolymers and hydrophobicity of the micelles were proven very important for the stabilization. A higher hydrophobicity of the micelle cores was expected to favor the entrapment of primary gold clusters and the stabilization of gold nanoparticles.     

Design of water-based ferrofluids as contrast agents for magnetic resonance imaging

We report the synthesis, characterization and relaxometric study of ferrofluids based on iron oxide, with potential for use as magnetic resonance imaging (MRI) contrast agents (CAs). The effect of different cost-effective, water-based surface modification approaches which can be easily scaled-up for the large scale synthesis of the ferrofluids has been investigated. Surface modification was achieved by silanization, and/or coating with non-toxic commercial dispersants (a lauric polysorbate and a block copolymer with pigment affinic groups, namely Tween 20 and Disperbyk 190) which were added after or during iron oxide nanoparticle synthesis. It was observed that all the materials synthesized functioned as negative contrast agents at physiological temperature and at frequencies covered by clinical imagers. The relaxometric properties of the magnetic nanoparticles were significantly improved after surface coating with stabilizers compared to the original iron oxide nanoparticles, with particular reference to the silica-coated magnetic nanoparticles. The results indicate that the optimization of the preparation of colloidal magnetic ferrofluids by surface modification is effective in the design of novel contrast agents for MRI by enabling better or more effective interaction between the coated iron oxide nanoparticles and protons present in their aqueous environment.     

Investigation of tannery liming waste water using green synthesised iron oxide nano particles

ABSTRACT

The present study aimed that non-toxic, less expensive, easily available, safer to environment and previously unreported Eclipta prostrata leaf extract is used for the green synthesis of iron oxide nano particles. The iron oxide nanoparticles (NPs) were characterised by UV–visible, Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tannery effluents treated by photodegradation process and the removal efficiency of chemical oxygen demand (COD), biological oxygen demand (BOD) and sulphide were analysed. The maximum removal efficiency correlated with operating parameters was explained using response surface methodology with Boxmen Beckmen design.     

Synthesis of atypical nanoparticles by the nanostructure in thin films of triblock copolymers

We report the synthesis of atypical nanoparticles in donut shape with or without additional spherical nanoparticles attached on them by using the donut-like nanostructure formed in a thin film of triblock copolymers. In a high-humidity condition, a spin-coated film of triblock copolymer had donut-like holes consisting of the periphery and the center. By selective coordination of precursors of nanoparticles to the periphery of the holes, donut-like oxide nanoparticles were synthesized by oxygen plasma treatment on the film. Moreover, we were able to attach spherical nanoparticles on the donut-like nanoparticles by incorporating the other type of precursors to the center of the holes. Thus, beyond the synthesis of typical spherical nanoparticles, the results here extend potentials of the block copolymer approach to control the shape and complexity of nanoparticles.     

Synthesis of aligned hematite nanoparticles on chitosan–alginate films

Iron oxide nanoparticles are being viewed with interest owing to the great potential they have in the biomedical applications like MRI contrast enhancement, targeted drug delivery, hyperthermia and recently in magnetic separation of cancer cells from the body. Templated synthesis has been considered ideal for synthesis of iron oxide nanoparticles as particles are attracted magnetically, in addition to usual flocculation through van der Waals attraction. Biological templates are attractive owing to their biocompatibility and the attractive porosity and surface chemistry that nature provides. Polysaccharides like chitosan and alginate have been employed in the synthesis of a polyion complex, which provided the active-binding sites for iron(II) ions in solution to bind. The natural organization of chitosan and alginate into a porous film has been exploited to synthesize spherical iron oxide nanoparticles through careful calcination of the iron(II) conjugate film. Our experiments indicate that the formed nanoparticles are highly crystalline, confirm to the hematite structure and have a superparamagnetic response with a low coercivity of 116 Oe. Particles thus synthesized were highly monodisperse with hydrodynamic diameter of 1.8 nm. The symmetric porosity of the film translates into the synthesis of well-aligned nanoparticles of iron oxide. Compared to synthesis in solution, the film-assisted synthesis offered a greater degree of control over the particle size distribution pattern, with the chitosan–alginate template providing the needed spatial separation to prevent the aggregation due to magnetostatic coupling. Such hematite nanoparticles can either be used directly or converted to paramagnetic magnetite by reduction. Zeta potential measurements indicate highly stable nanoparticles, which can therefore be conjugated to cationic liposomes carrying drugs and magnetically guided to target sites.     

纳米介孔氧化铁的制备*

纳米氧化铁的许多优异性能使其成为广泛的研究热点。本文介绍了纳米氧化铁的制备及其颗粒大小、形貌控制等方面的进展状况。综述了各种不同形态介孔氧化铁及含铁介孔纳米复合材料的研究进展,结合课题组的研究工作,重点评述了介孔氧化铁的制备进展,并对该领域的研究方向和需要解决的问题提出了自己的观点。     

Fe-containing nanocomposites based on a biocompatible copolymer 1-vinyl-1,2,4-triazole with <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone

New polymer nanocomposites containing iron oxide nanoparticles stabilized with a biocompatible copolymer of 1-vinyl-1,2,4-triazole with N-vinylpyrrolidone were produced. The synthesis was conducted using the method of chemical reduction of iron ions with hydrazine hydrate in an aqueous medium in the presence of a polymer matrix. The ESR spectroscopy data showed that the core—shell type nanoparticles were obtained. The core generally consistsed of zero-valence iron coated with an oxide shell. According to the data of transmission electron microscopy, the obtained polymer nanocomposites consisted of nanoparticles of mainly spherical shape with a diameter from 1 to 14 nm. Aggregates formed from individual stabilized nanoparticles of up to 75 nm in size (in most cases) were also observed. These aggregated particles were found to self-organize and form branched chains. Nanocomposites were characterized by a different particle-size distribution, which was determined by the initial ratio of the copolymer and the precursor of iron nanoparticles.     

Synthesis and characterization of cobalt ferrite nanoparticles in hybrid micelles of poly[styrene-<Emphasis Type="Italic">block</Emphasis>-(ethylene oxide)] and sodium dodecyl sulfate

Cobalt ferrite nanoparticles are synthesized in hybrid micelles of poly[styrene-block-(ethylene oxide)] and sodium dodecyl sulfate in water at room temperature. The nanoparticles are prepared by the chemical precipitation method via the exchange reaction between iron and cobalt salts with sodium dodecyl sulfate and the redox reaction under the action of an aqueous solution of methylamine. As evidenced by small-angle X-ray scattering, transmission electron microscopy, and ferromagnetic resonance examination, cobalt ferrite nanoparticles occurring in hybrid micelles of the block copolymer and sodium dodecyl sulfate are polydisperse (their size is 0.3–50 nm) and ferromagnetic.     

Optimization and ecofriendly synthesis of iron oxide nanoparticles as potential antioxidant

The present study involves the use of Box-Behnken design for optimization of the energy-efficient process variables, eco-friendly synthesis of nanoparticles of iron oxide using Coriandrum sativum L. (cilantro) leaf extract. The factors, which significantly influenced mean nanoparticle size, surface charge, and size distribution, were the volume of leaf extract, agitation speed, and temperature. The developed model using Box-Behnken design was validated by synthesizing the iron nanoparticles using optimized operational conditions i.e. 10 ml volume of leaf extract, 1500 rpm agitation speed and 30 °C temperature. This resulted in the formation of highly stable iron oxide nanoparticles with mean particle size 161.5 nm and polydispersity index 0.132 with a zeta potential of −19.5 mV. The free radical inhibitory activity of prepared iron oxide nanoparticles was found comparable to ascorbic acid. These results reveal that iron nanoparticles for a biomedical application can be prepared at ambient temperature in an eco-friendly manner.     

Nanometer metallic copper particle synthesis in reverse micelles

We describe the synthesis in situ of copper nanoparticles in reverse micelles. It is possible to form metallic particles either surrounded or not surrounded by an oxide layer.     

Synthesis of monodisperse biotinylated p(NIPAAm)-coated iron oxide magnetic nanoparticles and their bioconjugation to streptavidin

We describe here the synthesis of 10 nm, monodisperse, iron oxide nanoparticles that we have coated with temperature-sensitive, biotinylated p(NIPAAm) (b-PNIPAAm). The PNIPAAm was prepared by the reversible addition fragmentation chain transfer polymerization (RAFT), and one end was biotinylated with a PEO maleimide-activated biotin to form a stable thioether linkage. The original synthesized iron oxide particles were stabilized with oleic acid. They were dispersed in dioxane, and the oleic acid molecules were then reversibly exchanged with a mixture of PNIPAAm and b-PNIPAAm at 60 degrees C. The b-PNIPAAm-coated magnetic nanoparticles were found to have an average diameter of approximately 15 nm by dynamic light scattering and transmission electron microscopy. The ability of the biotin terminal groups on the b-PNIPAAm-coated nanoparticles to interact with streptavidin was confirmed by fluorescence and surface plasmon resonance. It was found that the b-PNIPAAm-coated iron oxide nanoparticles can still bind with high affinity to streptavidin in solution or when the streptavidin is immobilized on a surface. We have also demonstrated that the binding of the biotin ligands on the surface of the temperature-responsive magnetic nanoparticles to streptavidin can be turned on and off as a function of temperature.     

Chemical synthesis of magnetic nanoparticles

Recent advances in the synthesis of various magnetic nanoparticles using colloidal chemical approaches are reviewed. Typically, these approaches involve either rapid injection of reagents into hot surfactant solution followed by aging at high temperature, or the mixing of reagents at a low temperature and slow heating under controlled conditions. Spherical cobalt nanoparticles with various crystal structures have been synthesized by thermally decomposing dicobalt octacarbonyl or by reducing cobalt salts. Nanoparticles of Fe-Pt and other related iron or cobalt containing alloys have been made by simultaneously reacting their constituent precursors. Many different ferrite nanoparticles have been synthesized by the thermal decomposition of organometallic precursors followed by oxidation or by low-temperature reactions inside reverse micelles. Rod-shaped iron nanoparticles have been synthesized from the oriented growth of spherical nanoparticles, and cobalt nanodisks were synthesized from the thermal decomposition of dicobalt octacarbonyl in the presence of a mixture of two surfactants.     

Dissolution of iron oxide nanoparticles inside polymer nanocapsules

The structure of poly(organosiloxane) nanocapsules partially filled with iron oxide cores of different sizes was revealed by small angle X-ray scattering and X-ray diffraction. The nanocapsules are synthesized by the formation of a poly(organosiloxane) shell around iron oxide nanoparticles and the simultaneous partial dissolution of these cores. Due to the high scattering contrast of the iron oxide cores compared to the polymer shell, the particle size distribution of the cores inside the capsules can be measured by small angle X-ray scattering. Additional information can be revealed by X-ray diffraction, which gives insights into the formation of the polymer network and the structure of the iron oxide cores. The study shows how the crystallinity and size of the nanoparticles as well as the shape and width of the size distribution can be altered by the synthesis parameters.     

Hot-injection synthesis of iron/iron oxide core/shell nanoparticles for T2 contrast enhancement in magnetic resonance imaging

Here we report a new, bench-top synthesis for iron/iron oxide core/shell nanoparticles via the thermal decomposition of Fe(η(5)-C(6)H(3)Me(4))(2). The iron/iron oxide core/shell nanoparticles are superparamagnetic at room temperature and show improved negative contrast in T(2)-weighted MR imaging compared to pure iron oxides nanoparticles, and have a transverse relaxivity (r(2)) of 332 mM(-1) s(-1).     

Plasma-Induced Synthesis of CuO Nanofibers and ZnO Nanoflowers in Water

Fiber-shaped cupric oxide (CuO) nanoparticles and flower-shaped ZnO nanoparticles were facilely synthesized by plasma-induced technique directly from copper and zinc electrode pair in water, respectively. The phase composition, morphologies and optical property of nanoparticles have been investigated by energy dispersive X-ray analysis, X-ray powder diffraction, transmission electron microscopy and UV–vis. The in situ analysis by an optical emission spectroscopy clarified the formation mechanism. Plasma was generated from the discharge between a metal electrode pair in water by a pulse direct current power. CuO and ZnO nanoparticles were synthesized via almost the same formation mechanism, which were prepared via the rapid energetic radicals’ bombardment to electrodes’ surface, atom vapour diffusion, plasma expansion, solution medium condensation, and in situ oxygen reaction and further growth. This novel plasma-induced technique will become a potential application in nanomaterials synthesis.     

用于基因传输及磁共振显像的聚乙烯亚胺-g-聚己内酯共聚物的合成与表征

采用可生物降解的聚己内酯改性聚乙烯亚胺,得到两亲性的接枝共聚物(PEI-g-PCL).该共聚物通过溶剂挥发法在水中自组装形成纳米粒子,其内部负载有超顺磁性四氧化三铁纳米粒子(SPIO)及质粒DNA(pDNA).研究表明,PEI-g-PCL聚合物自组装形成的颗粒为胶束状,无论是否负载SPIO纳米粒子都可以有效地负载pDNA,并对293细胞具有较高的转染效率.此类载体有望在基因转染的过程中利用磁共振手段进行实时、无创观测.