Stabilization of Metal Nanoparticles in Aqueous Medium by Polyethyleneoxide-Polyethyleneimine Block Copolymers

The branched polyethyleneoxide-polyethyleneimine (PEO)n-b-PEI block copolymers are synthesized and fractionated. The (PEO)n-b-PEI block copolymers are found to be able to form micelles in aqueous solution after addition of certain metal compounds (H2PtCl6, Na2PtCl4, RhCl3). The degree of copolymer polydispersity seems to play an important role in metal nanoparticle stabilization. Comparison of diblock and branched copolymers shows that as a rule branched block copolymers are the better stabilizing systems for metal nanoparticles. In the case of micelle formation due to interaction with metal compounds, fine control on colloid morphology can be provided, which leads to very uniform particles. Variation of different parameters (such as concentration, pH, type of reducing agent) affects the nanoparticle morphology as well. Copyright 1999 Academic Press.     

Synthesis of nonspherical superparamagnetic particles: in situ coprecipitation of magnetic nanoparticles in microgels prepared by stop-flow lithography

We present the synthesis of nonspherical magnetic microparticles with multiple functionalities, shapes, and chemistries. Particle synthesis was performed in two steps: polymeric microparticles functionalized homogenously with carboxyl groups were generated using stop-flow lithography, and then in situ coprecipitation was used to grow magnetic nanoparticles at these carboxyl sites. With successive growth of magnetic nanoparticles, we obtained polymeric particles with saturation magnetizations of up to 42 emu/g microparticle. The growth in the magnetic nanoparticle mean size and polydispersity was determined from the magnetization curves obtained following each growth cycle; nanoparticle sizes were limited by the physical constraint of the effective mesh within the hosting gel microparticle. Particles with spatially segregated domains of varying magnetic properties (e.g., Janus particles, particles with step changes in magnetite concentration, etc.) can be synthesized readily using this approach.     

Polymer mediated self-assembly of magnetic nanoparticles

We present a simple polymer-mediated process of assembling magnetic FePt nanoparticles on a solid substrate. Alternatively absorbing the PEI molecule and FePt nanoparticles on a HO-terminated solid surface leads to a smooth FePt nanoparticle assembly with controlled assembly thickness and dimension. Magnetic measurements show that the thermally annealed FePt nanoparticle assembly as thin as three nanoparticle layers is ferromagnetic. The magnetization direction of this thin FePt nanoparticle assembly is readily controlled with the laser-assisted magnetic writing. The reported process can be applied to various substrates, nanoparticles, and functional macromolecules and will be useful for future magnetic nanodevice fabrication.     

Amine‐Functionalized Polyglycidyl Methacrylate Microsphere as a Unified Template for the Synthesis of Gold Nanoparticles and Single‐Crystal Gold Plates

Polyglycidyl methacrylate (PGMA) microspheres, crosslinked and surface‐functionalized by amine, can be used as a solid‐state template for the synthesis of gold (Au) crystals in the forms of either nanoparticles (NPs) or plates. It is discovered that the polymer microsphere acts as an internal template to cultivate Au NPs inside the microsphere or an external template to generate the single‐crystal plates depending on the critical concentration (C_cr) of gold ions. The ion–dipole interaction and the structure‐dependent solubility of gold induce two distinct gold nanostructures in the presence of the functionalized polymer microspheres. The catalytic activity and long‐term storage of the developed gold nanostructures that can be easily scaled‐up for mass production through the developed novel methodology is demonstrated.     

多嵌段共聚物/纳米粒子杂化多级结构的光学性能

结合耗散粒子动力学模拟和时域有限差分方法,研究了A(BC)_n多嵌段共聚物和纳米粒子共混体系的自组装行为及其光学性能,分析了纳米粒子体积分数和嵌段间相互作用强度对自组装形貌及其光学性能的影响。结果表明,A(BC)_n多嵌段共聚物/纳米粒子共混体系可形成有机/无机杂化的多级结构,改变纳米粒子的体积分数和嵌段间相互作用强度可以调控纳米粒子的分布及其相应的多级结构。不同尺度的结构对不同频率光的反射作用有明显区别,而纳米粒子的加入显著增大了反射峰的强度和宽度。改变纳米粒子的分布可调控反射峰的强度和宽度。     

Valence-controlled protein conjugation on nanoparticles via re-arrangeable multivalent interactions of tandem repeat protein chains

Precise control of the number of conjugated proteins on a nanoparticle surface has long been a highly challenging task. Here, we developed a one-pot, purification-free strategy for valency-controlled conjugation of tandem repeat protein chains on gold nanoparticles. Protein chains were designed to contain multiple, regularly spaced binding modules, which can multivalently interact with coating molecules on nanoparticle surfaces. We discovered that a slow increase of this interaction strength facilitates full participation of repeated binding modules on a protein chain for surface binding (as well as dynamic rearrangement) on a single nanoparticle, which resulted in stable protein chain wrapping around nanoparticles. By varying the protein chain length, a defined number of protein chains were conjugated on gold nanoparticles with difference sizes. Various high-order nanoparticle structures were accurately assembled with these valence-controlled protein–particle conjugates. The present strategy offers a highly dynamic but controlled protein coating approach on solid surfaces of diverse nanostructures. In addition, this work also provides a valuable clue to understand dynamic binding processes of multivalent repeat proteins.

Tandem repeat protein chains were wrapped around nanoparticles via re-arrangeable multivalent interactions for valence controlled protein conjugation.     

Shape‐Controlled Growth of Carbon Nanostructures: Yield and Mechanism

Carbon nanostructures with precisely controlled shapes are difficult materials to synthesize. A facet‐selective‐catalytic process was thus proposed to synthesize polymer‐linked carbon nanostructures with different shapes, covering straight carbon nanofiber, carbon nano Y‐junction, carbon nano‐hexapus, and carbon nano‐octopus. A thermal chemical vapor deposition process was applied to grow these multi‐branched carbon nanostructures at temperatures lower than 350 °C. Cu nanoparticles were utilized as the catalyst and acetylene as the reaction gas. The growth of those multi‐branched nanostructures was realized through the selective growth of polymer‐like sheets on certain indexed facets of Cu catalyst. The vapor–facet–solid (VFS) mechanism, a new growth mode, has been proposed to interpret such a growth in the steps of formation, diffusion, and coupling of carbon‐containing oligomers, as well as their final precipitation to form nanostructures on the selective Cu facets.     

Characterization of superparamagnetic "core-shell" nanoparticles and monitoring their anisotropic phase transition to ferromagnetic "solid solution" nanoalloys

The structure, magnetism, and phase transition of core-shell type CoPt nanoparticles en route to solid solution alloy nanostructures are systematically investigated. The characterization of Co(core)Pt(shell) nanoparticles obtained by a "redox transmetalation" process by transmission electron microscopy (TEM) and, in particular, X-ray absorption spectroscopy (XAS) provides clear evidence for the existence of a core-shell type bimetallic interfacial structure. Nanoscale phase transitions of the Co(core)Pt(shell) structures toward c-axis compressed face-centered tetragonal (fct) solid solution alloy CoPt nanoparticles are monitored at various stages of a thermally induced annealing process and the obtained fct nanoalloys show a large enhancement of their magnetic properties with ferromagnetism. The relationship between the nanostructures and their magnetic properties is in part elucidated through the use of XAS as a critical analytical tool.     

磁纳米探针检测人绒毛膜促性腺激素

采用链霉亲和素包被磁纳米粒子,将生物素标记的特异性抗体偶联在磁纳米粒子上,制备出高特异性的磁纳米探针;利用此探针对人绒毛膜促性腺激素(HCG)进行测定,建立了定量检测蛋白类激素的化学发光分析方法.利用紫外可见分光光度计、透射电镜及动态光散射仪对磁纳米探针进行表征,同时对化学发光实验条件进行优化.在2×10~(-4) mol/L鲁米诺、8×10~(-4) mol/L H_2O_2, pH=13的优化条件下,将磁纳米探针用于HCG的定量检测.结果表明,所测发光强度与待测HCG浓度之间线性相关,相关系数r为0.9924,线性检测范围由常规板式ELISA的5～200 μg/L扩展到0.5～250 μg/L;相对标准偏差为3.82%.采用本方法和常规ELISA法同时对34份人血清标本HCG进行测试,两者相关性良好.利用制备的磁纳米探针定量测定微量蛋白类激素,具有灵敏、高效、快捷、检测范围宽等优点,有望应用于其它微量蛋白的检测.     

Formation and morphological characteristics of selenium-containing nanostructures based on rigid-chain cellulose derivatives

Nanostructures arising from the reduction of ionic selenium by a selenite-ascorbate redox system in aqueous solutions of oxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose have been studied by using a set of optical methods (flow birefringence and static and dynamic light scattering) and viscometry. The adsorption of a substantial amount of macromolecules (up to 3200) on selenium nanoparticles has been experimentally discovered. This effect leads to the formation of superhigh-molecular-mass spherical nanostructures with a high density of the polymer shell. The thermodynamic state of solutions of nanostructures has been characterized. In the region of occurrence of stable dispersions, the values of the free energy of macromolecule-selenium nanoparticle interaction have been calculated for polymer nanostructures. Radii of amorphous selenium nanoparticles occurring in the nuclei of nanostructures and the thickness of the polymer shell have been estimated. Given the fixed molecular mass and comparable rigidity of a polymer matrix, the structure of the monomer unit of the cellulose derivative defines the morphology of the nanostructure being formed.     

Multicomponent nanoparticles via self-assembly with cross-linked block copolymer surfactants

We describe a simple and versatile protocol to prepare water-soluble multifunctional nanostructures by encapsulation of different nanoparticles in shell cross-linked, block copolymer micelles. This method permits simultaneous incorporation of different nanoparticle properties within a nanoscale micellar container. We have demonstrated the co-encapsulation of magnetic (gamma-Fe2O3 and Fe3O4), semiconductor (CdSe/ZnS), and metal (Au) nanoparticles in different combinations to form multicomponent micelles that retain the precursor particles' distinct properties. Because these multifunctional hybrid nanostructures spontaneously assemble from solution by simultaneous desolvation of nanoparticles and amphiphilic block copolymer components, we anticipate that this can be used as a general protocol for preparing multifunctional nanostructures without explicit multimaterial synthesis or surface functionalization of nanoparticles.     

Facile Synthesis of Multi-Branched Gold Nanostructures through a TBAB-Assisted Route in Aqueous Solution and Their SERS Property

Facile synthesis of multi‐branched gold nanostructures by using the tetrabutyl ammonium bromide (TBAB) as a capping agent is described. The reaction is carried out in a one‐step process at mild temperature. Gold nanostructures with more than six sharp branches ranging from 70 to 130 nm in length are synthesized in high yield. It is proposed that the relative weak adsorption capacity of TBAB leads to the incompletely covered gold surface and the growth of nanoparticles occurs on the uncovered gold surface, and therefore short branches appear consequently. Then positively charged TBAB layers on the gold surfaces prevent the branches from aggregating with each other which stimulates the branch growth. The prepared branched gold nanoparticles show efficient surface‐enhanced Raman scattering (SERS) properties. Low temperature (4°C) is unfavorable to the formation of multi‐branched gold nanostructures, and only thin small irregular plate‐like nanoparticles are produced. The addition of SDS in TBAB aqueous solution results in forming SDS micelles at much lower concentration of SDS (0.4 mmol/L) as compared to that in pure water, and short branched gold nanoparticles are obtained in the SDS‐TBAB system.     

聚苯胺/贵金属复合纳米材料的可控合成及催化应用

导电高分子/贵金属复合纳米材料因其在催化、传感、表面增强拉曼、光热治疗等诸多领域的应用前景而受到广泛关注.本文主要介绍我们课题组近年来利用可控合成策略制备的负载型和包埋型两种结构聚苯胺/贵金属复合纳米材料,以及利用复合纳米材料的结构和功能特性,对其在多相催化领域的应用、结构与催化性能之间构效关系的探索.     

A general method for the rapid synthesis of hollow metallic or bimetallic nanoelectrocatalysts with urchinlike morphology

We have reported a facile and general method for the rapid synthesis of hollow nanostructures with urchinlike morphology. In-situ produced Ag nanoparticles can be used as sacrificial templates to rapidly synthesize diverse hollow urchinlike metallic or bimetallic (such as Au/Pt) nanostructures. It has been found that heating the solution at 100 degrees C during the galvanic replacement is very necessary for obtaining urchinlike nanostructures. Through changing the molar ratios of Ag to Pt, the wall thickness of hollow nanospheres can be easily controlled; through changing the diameter of Ag nanoparticles, the size of cavity of hollow nanospheres can be facilely controlled; through changing the morphologies of Ag nanostructures from nanoparticle to nanowire, hollow Pt nanotubes can be easily designed. This one-pot approach can be extended to synthesize other hollow nanospheres such as Pd, Pd/Pt, Au/Pd, and Au/Pt. The features of this technique are that it is facile, quick, economical, and versatile. Most importantly, the hollow bimetallic nanospheres (Au/Pt and Pd/Pt) obtained here exhibit an area of greater electrochemical activity than other Pt hollow or solid nanospheres. In addition, the approximately 6 nm hollow urchinlike Pt nanospheres can achieve a potential of up to 0.57 V for oxygen reduction, which is about 200 mV more positive than that obtained by using a approximately 6 nm Pt nanoparticle modified glassy carbon (GC) electrode. Rotating ring-disk electrode (RRDE) voltammetry demonstrates that approximately 6 nm hollow Pt nanospheres can catalyze an almost four-electron reduction of O(2) to H(2)O in air-saturated H(2)SO(4) (0.5 M). Finally, compared to the approximately 6 nm Pt nanoparticle catalyst, the approximately 6 nm hollow urchinlike Pt nanosphere catalyst exhibits a superior electrocatalytic activity toward the methanol oxidation reaction at the same Pt loadings.     

Synthesis and assembly of gold nanoparticles in organized molecular films of gemini amphiphiles

Generation and assembly of gold nanostructures were investigated in the organized molecular films of a series of gemini amphiphiles. The chloroauric acid, dissolved in the aqueous subphase, was incorporated into the monolayers of the gemini amphiphiles containing ethyleneamine spacers through an interfacial assembly. The in situ formed complex monolayers were transferred onto solid substrates, and gold nanoparticles were generated in the film by a chemical or photochemical reduction. Discrete gold nanoparticles with an absorption maximum at 550 nm were generated in the films by photoirradiation, while different gold nanostructures were obtained by chemical reduction. Depending on the chemical reductant, various shape and assembly of gold nanostructures were obtained. When reduced by hydroquinone, a tree-branched assembly of the nanoparticles was obtained and the film showed a broad band centered at around 900 nm. When NaBH 4 was applied, crooked nanowires or assembly of nanoparticles were obtained, depending on concentration, and the film showed absorption at 569 or 600 nm. Furthermore, by combining the photochemical and chemical reduction methods, i.e., the chloroaurate ion-incorporated film was initially irradiated with UV light and then subjected to chemical reduction, the optical absorption of the formed gold nanostructures can be regulated.     

Tailoring the carbon nanostructures grown on the surface of Ni-Al bimetallic nanoparticles in the gas phase

A gas-phase, one-step method for producing various aerosol carbon nanostructures is described. The carbon nanostructures can be selectively tailored with either straight, coiled, or sea urchin-like structures by controlling the size of Ni-Al bimetallic nanoparticles and the reaction temperature. The carbon nanostructures were grown using both conventional spray pyrolysis and thermal chemical vapor deposition. Bimetallic nanoparticles with catalytic Ni (guest) and non-catalytic Al (host) matrix were reacted with acetylene and hydrogen gases. At the processing temperature range of 650-800 °C, high concentration straight carbon nanotubes (S-CNTs) with a small amount of coiled carbon nanotubes (C-CNTs) can be grown on the surface of seeded bimetallic nanoparticle size <100 nm, resulting from consumption of the melting Al matrix sites; sea urchin-like carbon nanotubes (SU-CNTs) of small diameter (～10±4 nm) can be grown on the bimetallic nanoparticle size >100 nm, resulting from the significant size reduction of the available Ni sites due to thermal expansion of molten Al matrix sites without consumption of Al matrix. However, at the processing temperature range of 500-650 °C, C-CNTs can be grown on the bimetallic nanoparticle size <100 nm due to the presence of Al matrix in the bimetallic nanoparticles; SU-CNTs of large diameter (～60±13 nm) can also be grown on the bimetallic nanoparticle size >100 nm due to the isolation of Ni sites in the Al matrix.     

Synthesis of monofunctionalized gold nanoparticles by fmoc solid-phase reactions

In this communication, solid-phase reactions for the synthesis of Lys-monofunctionalized gold nanoparticles are described. A controlled and selective fabrication of linear nanoparticle arrays can be achieved through peptide linkage systems, and therefore it is essential to prepare Fmoc amino acid nanoparticle building blocks susceptible to Fmoc solid-phase peptide synthesis. Gold nanoparticles containing carboxylic acids (2) in the organic shell were covalently ligated to Lys on solid supports through amide bond coupling reactions. We employed Fmoc-Lys-substituted polymer resins such as Fmoc-Lys-Wang or Fmoc-Lys-HMPA-PEGA. The low density of Lys on the matrix enabled 2 nm-sized gold nanoparticles to react with Lys in a 1:1 ratio. Subsequent cleavage reactions using 60% TFA reagent resulted in Lys transfer from the solid matrix to gold nanoparticles, and the Fmoc-Lys-monofunctionalized gold nanoparticles (5) were obtained with 3-15% yield. Synthesis using HMPA-PEGA resin increased productivity due to the superior swelling properties of PEGA resin in DMF. Monofunctionalization of nanoparticles was microscopically characterized using TEM for the ethylenediamine-bridged nanoparticle dimers (6). By counting the number of 6, we found that at least 60% of cleaved nanoparticles were monofunctionalized by Lys. This method is highly selective and efficient for the preparation of monofunctionalized nanoparticles.     

Functionalized surface as template for in situ generation of two-dimensional metal nanoparticle assembly

Two-dimensional gold nanoparticle assemblies with an average nanoparticle size of 6 nm are generated on silicon and indium tin oxide (ITO)-coated glass surfaces, functionalized with polyethylenimine (PEI) silane monolayer. Contact angle measurements show increased hydrophilic character of the surface due to nanoparticle formation. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) are used to monitor the chemical and structural development of these nanostructures, while UV–vis spectroscopy is used to follow the formation of the nanoparticle assemblies. This paper elucidates a simple route to in situ synthesis of surface immobilized gold nanoparticles under ambient conditions and also extends to the synthesis of other surface bound nanoparticles, like silver and platinum. Gold nanoparticle assemblies generated in this study are also catalytically active towards methanol oxidation reaction (MOR), which is relevant for direct methanol fuel cells (DMFCs).     

Establishment and implications of a characterization method for magnetic nanoparticle using cell tracking velocimetry and magnetic susceptibility modified solutions

Magnetic micro and nanoparticles conjugated to affinity labels have become a significant, commercial reagent. It has been demonstrated that the performance of cell separation systems using magnetic labels is a function of the magnitude of the magnetic force that can be generated through labeling. This magnetic force is proportional to the number of magnetic particles bound to the cell, the magnetic energy gradient, and the particle-field interaction parameter. This particle-field interaction parameter, which is the product of the relative volumetric, magnetic susceptibility and the volume of the micro or nanoparticle, is a fundamental parameter which can be used to characterize the magnetic particles. An experimental technique is presented which measures the volumetric magnetic susceptibility of particles through the use of susceptibility modified solutions and an experimental instrument, Cell Tracking Velocimetry, CTV. Experimental studies were conducted on polystyrene microspheres alone and those bound to four different magnetic nanoparticles. The experimentally determined values of the magnetic susceptibility of the polystyrene microspheres are consistent with values found from literature. Consequently, magnetic susceptibility measurements of these polystyrene microspheres bound with the magnetic nanoparticles combined with particle size measurements using commercial dynamic light scattering instrument allowed estimates of the particle-field interaction parameter to be made for four commercial, magnetic nanoparticles. The value found for MACS beads is close to what is reported from an independent study. The values for MACS beads and Imag beads are found to agree with what is observed from experiments. Finally, an experimental demonstration of the impact that differences in this field interaction parameter has on the labeling of human lymphocytes is presented.     

Supramolecular assembly of cyclodextrin-based nanoparticles on solid surfaces for gene delivery

In this work, a new approach for surface-mediated gene delivery based on inclusion complex formation between the solid surface and delivery vehicles is presented. beta-Cyclodextrin (CD) molecules form high-affinity inclusion complexes with adamantane. This complexation ability was used to specifically immobilize beta-CD-modified poly(ethylenimine) (CD-PEI) nanoparticles on adamantane- (AD-) modified self-assembled monolayers. To investigate the nanoparticle/surface interaction, CD-PEI-based and PEI-based nanoparticles were passed through a surface plasmon resonance flow cell containing the monolayers. CD-PEI nanoparticles are specifically immobilized on the chip surface by cyclodextrin-adamantane inclusion complex formation. Minimal nanoparticle adsorption was detected with PEI-based nanoparticles or on control surfaces. Competition studies with free cyclodextrins reveal that the multivalent interactions between CD-PEI nanoparticles and the adamantane-modified surface results in significantly higher binding affinity than single cyclodextrin-adamantane complexes. Immobilized nanoparticles were characterized by atomic force microscopy and quantified by fluorescence assay. Thus, the ability of CD-PEI nanoparticles to form inclusion complexes can be exploited to attain specific, high-affinity loading of delivery vehicles onto solid surfaces.