Analysis of surface structure and hydrogen/deuterium exchange of colloidal silica suspension by contrast-variation small-angle neutron scattering

The microscopic surface structure and hydrogen/deuterium exchange effect were investigated by contrast-variation small-angle neutron scattering (CV-SANS) for three different-sized amorphous colloidal silica aqueous suspensions. The results show that the fraction of hydrogen/deuterium exchange per nanoparticle, phiH/D, strongly depends on the size of silica nanoparticles. This finding supports that the hydrogen/deuterium exchange occurs exclusively within a finite surface layer of silica nanoparticles, while the inner component remained unchanged. Detailed analyses of the scattering intensity functions led to the estimation of (1) phiH/D and (2) the thickness of the surface layer as functions of the particle radius. The surface layer thickness was found to increase from 18 to 35 A with decreasing the particle radius from 165 to 71.2 A. The surface area per unit weight of silica estimated with the CV-SANS results are comparable to those reported in the literature.     

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.     

原位合成钴/还原氧化石墨烯纳米粒子催化氨硼烷制氢

采用简单的原位还原合成方法,利用具有温和还原性能的氨硼烷作为还原剂,在室温下一步还原氧化石墨烯和氯化钴混合溶液制备了还原氧化石墨烯负载钴纳米复合材料催化剂. 利用所制备的钴/还原氧化石墨烯催化剂催化氨硼烷水解制氢,发现钴/还原氧化石墨烯具有优异的催化性能. 相对于没有负载的钴纳米粒子以及采用硼氢化钠作为还原剂制备的钴/还原氧化石墨烯催化剂,采用氨硼烷还原制备的钴/还原氧化石墨烯催化剂表现出更加优越的催化性能. 动力学测试表明,钴/还原氧化石墨烯催化氨硼烷水解反应为零级反应,同时钴/还原氧化石墨烯催化剂催化氨硼烷水解反应的活化能为27.10 kJ·mol^-1,低于大部分已报道的其它催化剂,甚至一些贵金属催化剂的活化能. 钴/还原氧化石墨烯催化剂有着稳定的循环使用性,特别是其具有的磁性使得它能够直接从溶液中通过磁力回收,极具应用前景. 这种简单有效的合成方法有望推广到其它的金属-还原氧化石墨烯纳米复合材料体系.     

CoFe2O4-TiO2 and CoFe2O4-ZnO thin film nanostructures elaborated from colloidal chemistry and atomic layer deposition

CoFe(2)O(4)-TiO(2) and CoFe(2)O(4)-ZnO nanoparticles/film composites were prepared from directed assembly of colloidal CoFe(2)O(4) in a Langmuir-Blodgett monolayer and atomic layer deposition (ALD) of an oxide (TiO(2) or ZnO). The combination of these two methods permits the use of well-defined nanoparticles from colloidal chemistry, their assembly on a large scale, and the control over the interface between a ferrimagnetic material (CoFe(2)O(4)) and a semiconductor (TiO(2) or ZnO). Using this approach, architectures can be assembled with a precise control from the Angstrom scale (ALD) to the micrometer scale (Langmuir-Blodgett film). The resulting heterostructures present well-calibrated thicknesses. Electron microscopy and magnetic measurement studies give evidence that the size of the nanoparticles and their intrinsic magnetic properties are not altered by the various steps involved in the synthesis process. Therefore, the approach is suitable to obtain a layered composite with a quasi-monodisperse layer of ferrimagnetic nanoparticles embedded in an ultrathin film of semiconducting material.     

Palladium nanoparticles and nanowires deposited electrochemically: AFM and electrochemical characterization

Palladium nanoparticles and nanowires electrochemically deposited onto a carbon surface were studied using cyclic voltammetry, impedance spectroscopy and atomic force microscopy. The ex situ and in situ atomic force microscopy (AFM) topographic images showed that nanoparticles and nanowires of palladium were preferentially electrodeposited to surface defects on the highly oriented pyrolytic graphite surface and enabled the determination of the Pd nanostructure dimensions on the order of 50–150 nm. The palladium nanoparticles and nanowires electrochemically deposited onto a glassy carbon surface behave differently with respect to the pH of the electrolyte buffer solution. In acid or mild acid solutions under applied negative potential, hydrogen can be adsorbed/absorbed onto/into the palladium lattice. By controlling the applied negative potential, different quantities of hydrogen can be incorporated, and this process was followed, analysing the oxidation peak of hydrogen. It is also shown that the growth of the Pd oxide layer begins at negative potentials with the formation of a pre-monolayer oxide film, at a potential well before the hydrogen evolution region. At positive potentials, Pd(0) nanoparticles undergo oxidation, and the formation of a mixed oxide layer was observed, which can act as nucleation points for Pd metal growth, increasing the metal electrode surface coverage. Depending on thickness and composition, this oxide layer can be reversibly reduced. AFM images confirmed that the PdO and PdO₂ oxides formed on the surface may act as nucleation points for Pd metal growth, increasing the metal electrode surface coverage. Dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday.     

Optimal design and characterization of superparamagnetic iron oxide nanoparticles coated with polyvinyl alcohol for targeted delivery and imaging

Superparamagnetic iron oxide nanoparticles (SPION) with narrow size distribution and stabilized by polyvinyl alcohol (PVA) were synthesized. The particles were prepared by a coprecipitation technique using ferric and ferrous salts with a molar Fe3+/Fe2+ ratio of 2. Using a design of experiments (DOE) approach, the effect of different synthesis parameters (stirring rate and base molarity) on the structure, morphology, saturation magnetization, purity, size, and size distribution of the synthesized magnetite nanoparticles was studied by various analysis techniques including X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) with differential scanning calorimetry (DSC) measurements, vibrating-sample magnetometer (VSM), transmission electron microscopy (TEM), UV-visible, and Fourier transform infrared (FT-IR) spectrometer. PVA not only stabilized the colloid but also played a role in preventing further growth of SPION followed by the formation of large agglomerates by chemisorption on the surface of particles. A rich behavior in particle size, particle formation, and super paramagnetic properties is observed as a function of molarity and stirring conditions. The particle size and the magnetic properties as well as particle shape and aggregation (individual nanoparticles, magnetic beads, and magnetite colloidal nanocrystal clusters (CNCs) are found to be influenced by changes in the stirring rate and the base molarity. The formation of magnetic beads results in a decrease in the saturation magnetization, while CNCs lead to an increase in saturation magnetization. On the basis of the DOE methodology and the resulting 3-D response surfaces for particle size and magnetic properties, it is shown that optimum regions for stirring rate and molarity can be obtained to achieve coated SPION with desirable size, purity, magnetization, and shape.     

Bifunctional Submicron Colloidosomes Coassembled from Fluorescent and Superparamagnetic Nanoparticles

Colloidosomes are microcapsules consisting of nanoparticle shells. These microcarriers can be self‐assembled from a wide range of colloidal particles with selective chemical, physical, and morphological properties and show promise for application in the field of theranostic nanomedicine. Previous studies have mainly focused on fairly large colloidosomes (>1 μm) based on a single kind of particle; however, the intrinsic building‐block nature of this microcarrier has not been exploited so far for the introduction of tailored functionality at the nanoscale. We report a synthetic route based on interfacial shear rheology studies that allows the simultaneous incorporation of different nanoparticles with distinct physical properties, that is, superparamagnetic iron oxide and fluorescent silica nanoparticles, in a single submicron colloidosome. These tailor‐made microcapsules can potentially be used in various biomedical applications, including magnetic hyperthermia, magnetic particle imaging, drug targeting, and bioimaging.     

Long-Term Colloidally Stable Aqueous Dispersions of ≤5 nm Spinel Ferrite Nanoparticles

Applications in biomedicine and ferrofluids, for instance, require long-term colloidally stable, concentrated aqueous dispersions of magnetic, biocompatible nanoparticles. Iron oxide and related spinel ferrite nanoparticles stabilized with organic molecules allow fine-tuning of magnetic properties via cation substitution and water-dispersibility. Here, we synthesize≤5 nm iron oxide and spinel ferrite nanoparticles, capped with citrate, betaine and phosphocholine, in a one-pot strategy. We present a robust approach combining elemental (CHN) and thermal gravimetric analysis (TGA) to quantify the ratio of residual solvent molecules and organic stabilizers on the particle surface, being of particular accuracy for ligands with heteroatoms compared to the solvent. SAXS experiments demonstrate the long-term colloidal stability of our aqueous iron oxide and spinel ferrite nanoparticle dispersions for at least 3 months. By the use of SAXS we approved directly the colloidal stability of the nanoparticle dispersions for high concentrations up to 100 g L⁻¹.     

New insights into the adsorption of 3-(trimethoxysilyl)propylmethacrylate on hydroxylated ZnO nanopowders

Functionalization of zinc oxide (ZnO) nano-objects by silane grafting is an attractive method to provide nanostructured materials with a variety of surface properties. Active hydroxyl groups on the oxide surface are one of the causes governing the interfacial bond strength in nanohybrid particles. Here, "as-prepared" and commercially available zinc oxide nanopowders with a wide range of surface hydroxyl density were functionalized by a well-known polymerizable silane coupling agent, i.e., 3-(trimethoxysilyl)propylmethacrylate (MPS). Fourier transform infrared (FTIR) and solid-state (13)C and (29)Si nuclear magnetic resonance (NMR) spectroscopic investigations demonstrated that the silane coupling agent was fully hydrolyzed and linked to the hydroxyl groups already present on the particle surface through covalent and hydrogen bonds. Due to a basic catalyzed condensation of MPS with water, a siloxane layer was shown to be anchored to the nanoparticles through mono- and tridentate structures. Quantitative investigations were performed by thermogravimetric (TGA) and elemental analyses. The amount of silane linked to ZnO particles was shown to be affected by the amount of isolated hydroxyl groups available to react on the particle surface. For as-prepared ZnO nanoparticles, the number of isolated and available hydroxyl groups per square nanometer was up to 3 times higher than the one found on commercially available ZnO nanoparticles, leading to higher amounts of polymerizable silane agent linked to the surface. The MPS molecules were shown to be mainly oriented perpendicular to the oxide surface for all the as-prepared ZnO nanoparticles, whereas a parallel orientation was found for the preheated commercially ZnO nanopowders. In addition, ZnO nanoparticles were shown to be hydrophobized by the MPS treatment with water contact angles higher than 60°.     

Field-assisted organization,substrate effects and magnetic behavior of Ag30Co70 core–shell nanoparticles

In core–shell systems with non-magnetic core and magnetic shell, the electron transport and magnetic properties are expected to show enhanced behavior due to the particular morpho-structural features of the conductive and magnetic regions. This may lead to novel advanced GMR materials and spin valves. This is the case of core–shell Ag–Co colloidal nanoscale particles that organize into regular arrays. An insight on the structure and morphology of the newly synthesized Ag–Co nanoparticles deposited on different substrates will be presented. The influence of the substrate on different morphologies and organization dynamics is discussed. It is shown that the magnetic behavior of the Ag–Co nanoparticles is highly influenced by the corona-like morphology of Co shell, chemical environment of the magnetic atoms and by the fact that they exhibit strongly reduced coordination due to the surface states.     

Physical and Chemical Properties of Magnetite and Magnetite-Polymer Nanoparticles and Their Colloidal Dispersions

The properties of polymer-coated magnetite nanoparticles, which have the potential to be used as effective magnetic resonance contrast agents, have been studied. The magnetite particles were synthesized by using continuous synthesis in an aqueous solution. The polymer-coated magnetite nanoparticles were synthesized by seed precipitation polymerization of methacrylic acid and hydroxyethyl methacrylate in the presence of the magnetite nanoparticles. The particle size was measured by laser light scattering. It was shown that the particle size, variance, magnetic properties, and stability of aqueous magnetite colloidal dispersion strictly depend on the nature of the stabilizing agent. The average hydrodynamic radius of the magnetite particles was found to be 5.7 nm in the stable aqueous colloidal dispersion. An inclusion of the magnetite particle into a hydrophilic polymeric shell increases the stability of the dispersion and decreases the influence of the stabilizing agent on the magnetic and structural properties of the magnetite particles as was shown by X-ray diffraction and M?ssbauer and IR spectroscopy, as well as by vibrating sample magnetometry. The variation in the polymeric shell size and the polymer net density can be useful tools for evaluation of the polymer-coated magnetite particles as effective contrast agents. Copyright 1999 Academic Press.     

Preparation of high-quality colloidal mask for nanosphere lithography by a combination of air/water interface self-assembly and solvent vapor annealing

Nanosphere lithography (NSL) has been regarded as an inexpensive, inherently parallel, high-throughput, materials-general approach to the fabrication of nanoparticle arrays. However, the order of the resulting nanoparticle array is essentially dependent on the quality of the colloidal monolayer mask. Furthermore, the lateral feature size of the nanoparticles created using NSL is coupled with the diameter of the colloidal spheres, which makes it inconvenient for studying the size-dependent properties of nanoparticles. In this work, we demonstrate a facile approach to the fabrication of a large-area, transferrable, high-quality latex colloidal mask for nanosphere lithography. The approach is based on a combination of the air/water interface self-assembly method and the solvent-vapor-annealing technique. It enables the fabrication of colloidal masks with a higher crystalline integrity compared to those produced by other strategies. By manipulating the diameter of the colloidal spheres and precisely tuning the solvent-vapor-annealing process, flexible control of the size, shape, and spacing of the interstice in a colloidal mask can be realized, which may facilitate the broad use of NSL in studying the size-, shape-, and period-dependent optical, magnetic, electronic, and catalytic properties of nanomaterials.     

表面修饰的二氧化锡纳米粒子的制备及微结构表征

采用胶体化学制得表面包覆有ＤＢＳ的二氧化锡纳米粒子，并运用一系列手段对其微结构进行了表征。     

Bioactivation and cell targeting of semiconductor CdSe/ZnS nanocrystals with phytochelatin-related peptides

Synthetic phytochelatin-related peptides are used as an organic coat on the surface of colloidal CdSe/ZnS semiconductor nanocrystals synthesized from hydrophobic coordinating trioctyl phosphine oxide (TOPO) solvents. The peptides are designed to bind to the nanocrystals via a C-terminal adhesive domain. This adhesive domain, composed of multiple repeats of cysteines pairs flanked by hydrophobic 3-cyclohexylalanines, is followed by a flexible hydrophilic linker domain to which various bio-affinity tags can be attached. This surface coating chemistry results in small, buffer soluble, monodisperse peptide-coated nanoparticles with high colloidal stability and ensemble photophysical properties similar to those of TOPO-coated nanocrystals. Various peptide coatings are used to modulate the nanocrystal surface properties and to bioactivate the nanoparticles. CdSe/ZnS nanocrystals coated with biotinylated peptides efficiently bind to streptavidin and are specifically targeted to GPI-anchored avidin-CD14 chimeric proteins expressed on the membranes of live HeLa cells. This peptide coating surface chemistry provides a novel approach for the production of biocompatible photoluminescent nanocrystal probes.     

Highly transparent silica monoliths embedded with high concentration oxide nanoparticles

Silica monoliths embedded with high concentration of γ-Fe₂O₃ or TiO₂ nanoparticles were prepared by a sol–gel procedure designed according to the inherent properties of oxide colloids. In the first step, highly dispersible oxide nanoparticles were produced using an in situ modification sol–gel strategy. Then, these particles were re-dispersed in silicon alkoxide-containing solution to form a stable colloidal solution. The hydrolysis and condensation reactions of alkoxide were catalyzed by an organic base (morpholine). Due to the large molecule size of morpholine, the electric double layer on the surface of colloidal particles was not compressed by the ionized morpholine molecules. The colloidal solution thus remained stable during the gelation process. Through this procedure, oxide nanoparticles could be immobilized homogeneously in the pores of a silica matrix, forming highly transparent and crack-free monoliths.     

The kinetics of low-temperature oxidation of cobalt nanoparticles on a carbon carrier

Size effects were found to influence the low-temperature oxidation of Co nanoparticles. These effects were likely caused by the predominant formation of oxide phase nuclei on edge and vertex Co nanocrystal atoms. The initial rate of oxidation was proportional to the degree of nanoparticle surface coverage with atomic oxygen. The magnetic method was used to determine the size of Co nanoparticles. The results were close to those obtained by transmission electron microscopy.     

Magnetic Fe2O3-polystyrene/PPy core/shell particles: bioreactivity and self-assembly

This paper describes the synthesis of new magnetic, reactive polystyrene/polypyrrole core/shell latex particles. The core consists of a polystyrene microsphere containing gamma-Fe2O3 superparamagnetic nanoparticles (PSmag), and the shell is made of reactive N-carboxylic acid-functionalized polypyrrole (PPyCOOH). These PSmag-PPyCOOH latex particles, average diameter 220 nm, were prepared by copolymerization of pyrrole (Py) and the active carboxyl-functionalized pyrrole (PyCOOH) in the presence of PSmag particles. PNVP was used as a steric stabilizer. The functionalized polypyrrole-coated PSmag particles were characterized in terms of their particle size, surface morphology, chemical composition, and electrochemical and magnetic properties using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and SQUID magnetometry. Activation of the particle surface carboxyl groups was achieved using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS), which helps transform the carboxyl groups into activated ester groups (NSE). The activated particles, PSmag-PPyNSE, were further evaluated as bioadsorbents of biotin used as a model biomolecule. It was shown that biotin was immobilized at the surface of the PSmag-PPyNSE particles by forming interfacial amide groups. The assemblies of PSmag-PPyCOOH particles on glass plates were further investigated. When no magnetic field is applied, the particles assemble into 3D colloidal crystals. In contrast, under a magnetic field, one-particle-thick chains gathered in hedgehog-like architectures are obtained. Furthermore, PSmag-PPyCOOH coated ITO electrodes were shown to be electroactive and electrochemically stable, thus offering potentialities for creating novel high-specific-area materials for biosensing devices where the conducting polymer component would act as the transducer through its conductive properties.     

Quantitative Evaluation of the Total Magnetic Moments of Colloidal Magnetic Nanoparticles: A Kinetics‐based Method

A kinetics‐based method is proposed to quantitatively characterize the collective magnetization of colloidal magnetic nanoparticles. The method is based on the relationship between the magnetic force on a colloidal droplet and the movement of the droplet under a gradient magnetic field. Through computational analysis of the kinetic parameters, such as displacement, velocity, and acceleration, the magnetization of colloidal magnetic nanoparticles can be calculated. In our experiments, the values measured by using our method exhibited a better linear correlation with magnetothermal heating, than those obtained by using a vibrating sample magnetometer and magnetic balance. This finding indicates that this method may be more suitable to evaluate the collective magnetism of colloidal magnetic nanoparticles under low magnetic fields than the commonly used methods. Accurate evaluation of the magnetic properties of colloidal nanoparticles is of great importance for the standardization of magnetic nanomaterials and for their practical application in biomedicine.     

Dual magnetic-/temperature-responsive nanoparticles for microfluidic separations and assays

A stimuli-responsive magnetic nanoparticle system for diagnostic target capture and concentration has been developed for microfluidic lab card settings. Telechelic poly(N-isopropylacrylamide) (PNIPAAm) polymer chains were synthesized with dodecyl tails at one end and a reactive carboxylate at the opposite end by the reversible addition fragmentation transfer technique. These PNIPAAm chains self-associate into nanoscale micelles that were used as dimensional confinements to synthesize the magnetic nanoparticles. The resulting superparamagnetic nanoparticles exhibit a gamma-Fe2O3 core ( approximately 5 nm) with a layer of carboxylate-terminated PNIPAAm chains as a corona on the surface. The carboxylate group was used to functionalize the magnetic nanoparticles with biotin and subsequently with streptavidin. The functionalized magnetic nanoparticles can be reversibly aggregated in solution as the temperature is cycled through the PNIPAAm lower critical solution temperature (LCST). While the magnetophoretic mobility of the individual nanoparticles below the LCST is negligible, the aggregates formed above the LCST are large enough to respond to an applied magnetic field. The magnetic nanoparticles can associate with biotinylated targets as individual particles, and then subsequent application of a combined temperature increase and magnetic field can be used to magnetically separate the aggregated particles onto the poly(ethylene glycol)-modified polydimethylsiloxane channel walls of a microfluidic device. When the magnetic field is turned off and the temperature is reversed, the captured aggregates redisperse into the channel flow stream for further downstream processing. The dual magnetic- and temperature-responsive nanoparticles can thus be used as soluble reagents to capture diagnostic targets at a controlled time point and channel position. They can then be isolated and released after the nanoparticles have captured target molecules, overcoming the problem of low magnetophoretic mobility of the individual particle while retaining the advantages of a high surface to volume ratio and faster diffusive properties during target capture.     

Surface chemistry: a non-negligible parameter in determining optical properties of small colloidal metal nanoparticles

Surface chemistry can become pronounced in determining the optical properties of colloidal metal nanoparticles as the nanoparticles become so small (diameters <20 nm) that the surface atoms, which can undergo chemical interactions with the environment, represent a significant fraction of the total number of atoms although this effect is often ignored. For instance, formation of chemical bonds between surface atoms of small metal nanoparticles and capping molecules that help stabilize the nanoparticles can reduce the density of conduction band electrons in the surface layer of metal atoms. This reduced electron density consequently influences the frequency-dependent dielectric constant of the metal atoms in the surface layer and, for sufficiently high surface to volume ratios, the overall surface plasmon resonance (SPR) absorption spectrum. The important role of surface chemistry is highlighted here by carefully analyzing the classical Mie theory and a multi-layer model is presented to produce more accurate predictions by considering the chemically reduced density of conduction band electrons in the outer shell of metal atoms in nanoparticles. Calculated absorption spectra of small Ag nanoparticles quantitatively agree with the experimental results for our monodispersed Ag nanoparticles synthesized via a well-defined chemical reduction process, revealing an exceptional size-dependence of absorption peak positions: the peaks first blue-shift followed by a turnover and a dramatic red-shift as the particle size decreases. A comprehensive understanding of the relationship between surface chemistry and optical properties is beneficial to exploit new applications of small colloidal metal nanoparticles, such as colorimetric sensing, electrochromic devices, and surface enhanced spectroscopies.