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1.
Metamolecules and crystals consisting of nanoscale building blocks offer rich models to study colloidal chemistry, materials science, and photonics. Herein we demonstrate the self‐assembly of colloidal Ag nanoparticles into quasi‐one‐dimensional metamolecules with an intriguing self‐healing ability in a linearly polarized optical field. By investigating the spatial stability of the metamolecules, we found that the origin of self‐healing is the inhomogeneous interparticle electrodynamic interactions enhanced by the formation of unusual nanoparticle dimers, which minimize the free energy of the whole structure. The equilibrium configuration and self‐healing behavior can be further tuned by modifying the electrical double layers surrounding the nanoparticles. Our results reveal a unique route to build self‐healing colloidal structures assembled from simple metal nanoparticles. This approach could potentially lead to reconfigurable plasmonic devices for photonic and sensing applications.  相似文献   

2.
The use of a thiol‐functionalized nonionic surfactant to stabilize spherical gold nanoparticles in water induces the spontaneous formation of polyrotaxanes at the nanoparticle surface in the presence of the macrocycle α‐cyclodextrin. Whereas using an excess of surfactant an amorphous gold nanocomposite is obtained, under controlled drying conditions the self‐assembly between the surface supramolecules provides large and homogenous supercrystals with hexagonal close packing of nanoparticles. Once formed, the self‐assembled supercrystals can be fully redispersed in water. The reversibility of the crystallization process may offer an excellent reusable material to prepare gold nanoparticle inks and optical sensors with the potential to be recovered after use.  相似文献   

3.
Water vapor is ubiquitous under ambient conditions and may alter the shape of nanoparticles. How to utilize water adsorption for nanomaterial functionality and structure formation, however, is a yet unexplored field. Herein, we report the use of water vapor to induce the self‐organization of MgO nanocubes into regularly staggered one‐dimensional structures. This transformation evolves via an initial alignment of the MgO cubes, the formation of intermediate elongated Mg(OH)2 structures, and their reconversion into MgO cubes arranged in staggered structures. Ab initio DFT modelling identifies surface‐energy changes associated with the cube surface hydration and hydroxylation to promote the uncommon staggered stacked assembly of the cubes. This first observation of metal oxide nanoparticle self‐organization occurring outside a bulk solution may pave novel routes for inducing texture in ceramics and represents a great test‐bed for new surface‐science concepts.  相似文献   

4.
The self‐assembly of dispersed polymer‐coated ferromagnetic nanoparticles into micron‐sized one‐dimensional mesostructures at a liquid–liquid interface was reported. When polystyrene‐coated Co nanoparticles (19 nm) are driven to an oil/water interface under zero‐field conditions, long (≈ 5 μm) chain‐like assemblies spontaneously form because of dipolar associations between the ferromagnetic nanoparticles. Direct imaging of the magnetic assembly process was achieved using a recently developed platform consisting of a biphasic oil/water system in which the oil phase was flash‐cured within 1 s upon ultraviolet light exposure. The nanoparticle assemblies embedded in the crosslinked phase were then imaged using atomic force microscopy. The effects of time, temperature, and colloid concentration on the self‐assembly process of dipolar nanoparticles were then investigated. Variation of either assembly time t or temperature T was found to be an interchangeable effect in the 1D organization process. Because of the dependence of chain length on the assembly conditions, we observed striking similarities between 1D nanoparticle self‐assembly and polymerization of small molecule monomers. This is the first in‐depth study of the parameters affecting the self‐assembly of dispersed, dipolar nanoparticles into extended mesostructures in the absence of a magnetic field. © 2008 Wiley Periodicals, Inc.* J Polym Sci Part B: Polym Phys 46: 2267–2277, 2008  相似文献   

5.
Cationic gold nanoparticles offer intriguing opportunities as drug carriers and building blocks for self‐assembled systems. Despite major progress on gold nanoparticle research in general, the synthesis of cationic gold particles larger than 5 nm remains a major challenge, although these species would give a significantly larger plasmonic response compared to smaller cationic gold nanoparticles. Herein we present the first reported synthesis of cationic gold nanoparticles with tunable sizes between 8–20 nm, prepared by a rapid two‐step phase‐transfer protocol starting from simple citrate‐capped particles. These cationic particles form ordered self‐assembled structures with negatively charged biological components through electrostatic interactions.  相似文献   

6.
A limiting factor of solvent‐induced nanoparticle self‐assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions.  相似文献   

7.
Inverse opal films with unique optical properties have potential as photonic crystal materials and have stimulated wide interest in recent years. Herein, iridescent hybrid polystyrene/nanoparticle macroporous films have been prepared by using the breath‐figure method. The honeycomb‐patterned thin films were prepared by casting gold nanoparticle‐doped polystyrene solutions in chloroform at high relative humidity. Highly ordered hexagonal arrays of monodisperse pores with an average diameter of 880 nm are obtained. To account for the observed features, a microscopic phase separation of gold nanoparticles is proposed to occur in the breath‐figure formation. That is, individual gold nanoparticles adsorb at the solution/water interface and effectively stabilize condensed water droplets on the solution surface in a hexagonal array. Alternatively, at high nanoparticle concentrations the combination of breath‐figure formation and nanoparticle phase separation leads to hierarchical structures with spherical aggregates under a honeycomb monolayer. The films show large features in both the visible and NIR regions that are attributed to a combination of nanoparticle and ordered‐array absorptions. Organic ligand‐stabilized CdSe/CdS quantum dots or Fe3O4 nanoparticles may be loaded into the honeycomb structure to further modify the films. These results demonstrate new methods for the fabrication and functionalization of inverse opal films with potential applications in photonic and microelectronic materials.  相似文献   

8.
Adding colloidal nanoparticles into liquid‐crystal media has become a promising pathway either to enhance or to introduce novel properties for improved device performance. Here we designed and synthesized new colloidal hybrid silica nanoparticles passivated with a mesogenic monolayer on the surface to facilitate their organo‐solubility and compatibility in a liquid‐crystal host. The resulting nanoparticles were identified by 1H NMR spectroscopy, TEM, TGA, and UV/Vis techniques, and the hybrid nanoparticles were doped into a dual‐frequency cholesteric liquid‐crystal host to appraise both their compatibility with the host and the effect of the doping concentration on their electro‐optical properties. Interestingly, the silica‐nanoparticle‐doped liquid‐crystalline nanocomposites were found to be able to dynamically self‐organize into a helical configuration and exhibit multi‐stability, that is, homeotropic (transparent), focal conic (opaque), and planar states (partially transparent), depending on the frequency applied at sustained low voltage. Significantly, a higher contrast ratio between the transparent state and scattering state was accomplished in the nanoparticle‐embedded liquid‐crystal systems.  相似文献   

9.
CdS nanoparticles were formed on the surface of silica microspheres by the improved layer‐by‐layer self‐assembled technique. High‐resolution electron microscope (HRTEM) image and energy dispersive x‐ray analysis (EDX) confirmed formation of a quasi‐continuous CdS nanoparticles film on the silica microspheres. The results of UV‐vis and fluorescence spectra display that the spherical silica surface has a great effect on the photoluminescence of the loaded CdS nanoparticles. In contrast to the CdS nanoparticles powder, the composite can exhibit the emission ascribed to the band gap transition when the CdS nanoparticles film is relatively thick. This phenomenon is probably due to an enhancement of the crystallinity of CdS nanoparticles induced by the silica spheres.  相似文献   

10.
We report a new method in which spontaneous self‐assembly is employed to synthesize monodisperse polymer nanoparticles with controlled size (<50 nm), shape, tunable functionality, and enhanced solvent and thermal stability. Cooperative noncovalent interactions, such as hydrogen bonding and aromatic π–π stacking, assist self‐assembly of amphiphilic macromolecules (polystyrene‐block‐polyvinylpyridine, PS? PVP) and structure directing agents (SDAs) to form both spherical and anisotropic solid polymer nanoparticles with SDAs residing in the particle core surrounded by the polymers. Through detailed investigations by scanning electron microscopy and transmission electron microscopy (TEM), we have rationalized nanoparticle morphology evolution and dependence on factors such as SDA concentration and PVP size. By keeping the PS chain size constant, the particle morphology progresses from continuous films to spherical particles, and on to cylindrical nanowires or rods with increasing the PVP chain size. The final nanoparticles are very stable and can be redispersed in common solvents to form homogenous solutions and thin films of ordered nanoparticle arrays through solvent evaporation processes. These nanoparticles exhibit tunable fluorescent colors (or emissions) depending on the choices of the central SDAs. Our method is simple and general without requiring complicated synthetic chemistry, stabilizing surfactants, or annealing procedures (e.g., temperature or solvent annealing), making scalable synthesis feasible.  相似文献   

11.
Condensate microdrop self‐propelling (CMDSP) surfaces have attracted intensive interest. However, it is still challenging to form metal‐based CMDSP surfaces. We design and fabricate a type of copper‐based CMDSP porous nanoparticle film. An electrodeposition method based on control over the preferential crystal growth of isotropic nanoparticles and synergistic utilization of tiny hydrogen bubbles as pore‐making templates is adopted for the in situ growth of cerium oxide porous nanoparticle films on copper surfaces. After characterizing their microscopic morphology, crystal structure and surface chemistry, we explore their CMDSP properties. The nanostructure can realize the efficient ejection of condensate microdrops with sizes below 50 μm.  相似文献   

12.
We have demonstrated a novel way to form thickness‐controllable polyelectrolyte‐film/nanoparticle patterns by using a plasma etching technique to form, first, a patterned self‐assembled monolayer surface, followed by layer‐by‐layer assembly of polyelectrolyte‐films/nanoparticles. Octadecyltrimethoxysilane (ODS) and (3‐aminopropyl)triethoxysilane (APTES) self‐assembled monolayers (SAMs) were used for polyelectrolyte‐film and nanoparticle patterning, respectively. The resolution of the proposed patterning method can easily reach approximately 2.5 μm. The height of the groove structure was tunable from approximately 2.5 to 150 nm. The suspended lipid membrane across the grooves was fabricated by incubating the patterned polyelectrolyte groove arrays in solutions of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPC) giant unilamellar vesicles (GUVs). The method demonstrated here reveals a new path to create patterned 2D or 3D structures.  相似文献   

13.
A micro‐beam scanning X‐ray photoelectron spectroscopy (XPS) has been utilized to obtain information about the attachment of ligand to nanoparticles in solution by measuring the ligand components relative to nanoparticle components. CdSe/ZnS core/shell nanoparticles capped with three different kinds of ligand molecules are drop‐casted on a substrate and led to dry into self‐agglomerated micropatterns. Those specimens are mapped out by element‐sensitive XPS imaging. The spatial correlation between surface ligand molecules and core nanoparticle atoms is statistically analysed using Pearson correlation function, which provides with a useful assessment of the ligand binding to nanoparticle surfaces. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

14.
Inorganic nanoparticles have become a research focus in numerous fields because of their unique properties that distinguish them from their bulk counterparts. Controlling the size and shape of nanoparticles is an essential aspect of nanoparticle synthesis. Preparing inorganic nanoparticles by using block copolymer templates is one of the most reliable routes for tuning the size and shape of nanoparticles with a high degree of precision. In this Review, we discuss recent progress in the design of block copolymer templates for crafting spherical inorganic nanoparticles including compact, hollow, and core–shell varieties. The templates are divided into two categories: micelles self‐assembled from linear block copolymers and unimolecular star‐shaped block copolymers. The precise control over the size and morphology of nanoparticles is highlighted as well as the useful properties and applications of such inorganic nanoparticles.  相似文献   

15.
Polymerization‐induced self‐assembly (PISA) mediated by reversible addition–fragmentation chain transfer (RAFT) polymerization offers a platform technology for the efficient and versatile synthesis of well‐defined sterically stabilized block copolymer nanoparticles. Herein we synthesize a series of such nanoparticles with tunable anionic charge density within the stabilizer chains, which are prepared via statistical copolymerization of anionic 2‐(phosphonooxy)ethyl methacrylate (P) with non‐ionic glycerol monomethacrylate (G). Systematic variation of the P/G molar ratio enables elucidation of the minimum number of phosphate groups per copolymer chain required to promote nanoparticle occlusion within a model inorganic crystal (calcite). Moreover, the extent of nanoparticle occlusion correlates strongly with the phosphate content of the steric stabilizer chains. This study is the first to examine the effect of systemically varying the anionic charge density of nanoparticles on their occlusion efficiency and sheds new light on maximizing the loading of guest nanoparticles within calcite host crystals.  相似文献   

16.
Magnetic and fluorescent assemblies of iron‐oxide nanoparticles (NPs) were constructed by threading a viologen‐based ditopic ligand, DPV2+, into the cavity of cucurbituril (CB[7]) macrocycles adsorbed on the surface of the NPs. Evidence for the formation of 1:2 inclusion complexes that involve DPV2+ and two CB[7] macrocycles was first obtained in solution by 1H NMR and emission spectroscopy. DPV2+ was found to induce self‐assembly of nanoparticle arrays (DPV2+?CB[7]NPs) by bridging CB[7] molecules on different NPs. The resulting viologen‐crosslinked iron‐oxide nanoparticles exhibited increased saturation magnetization and emission properties. This facile supramolecular approach to NP self‐assembly provides a platform for the synthesis of smart and innovative materials that can achieve a high degree of functionality and complexity and that are needed for a wide range of applications.  相似文献   

17.
A new prototype of reversible self‐assembly between functionalized gold and titanium dioxide nanoparticles (NPs) utilizing hydrogen bonding interactions was developed and established. The gold nanoparticles were functionalized with a Hamilton‐receptor functionality bearing a thiol moiety as anchoring group. The titanium dioxide nanoparticles were modified with cyanurate derivatives which contained phosphonic acids as anchoring groups. The host–guest type interaction between two functionalized nanoparticles yielded a highly integrated nanoparticle system in chloroform. Moreover, by presenting a competing ligand in an exchange reaction, the product of self‐assembly can be segregated into the individual soluble components of functionalized nanoparticles. The self‐assembly and the exchange reaction were followed and monitored in detail by UV/Vis spectroscopy. The structure of the self‐assembly product was investigated using scanning electron microscopy (SEM) and small‐angle X‐ray scattering (SAXS).  相似文献   

18.
Self‐assembly of nanomaterials to yield a wide diversity of high‐order structures, materials, and devices promises new opportunities for various technological applications. Herein, we report that crack formation can be effectively harnessed by elaborately restricting the drying of colloidal suspension using a flow‐enabled self‐assembly (FESA) strategy to yield large‐area periodic cracks (i.e., microchannels) with tunable spacing. These uniform microchannels can be utilized as a template to guide the assembly of Au nanoparticles, forming intriguing nanoparticle threads. This strategy is simple and convenient. As such, it opens the possibility for large‐scale manufacturing of crack‐based or crack‐derived assemblies and materials for use in optics, electronics, optoelectronics, photonics, magnetic device, nanotechnology, and biotechnology.  相似文献   

19.
A poly[(2‐ethyl‐2‐oxazoline)‐ran‐(2‐nonyl‐2‐oxazoline)] copolymer in combination with hydroxypropylated cyclodextrins has been demonstrated to lead to a supramolecular self‐assembly process that results in the formation of kinetically trapped thermoresponsive nanoparticles. Selection of the cyclodextrin type provides control over the nanoparticle phase‐transition thermodynamics, thus affording optical temperature sensors with an unprecedented, long‐term thermal memory function, which is reversible or irreversible. This research also sheds light onto kinetic and dynamic supramolecular assemblies, thus providing important insight because similar supramolecular processes are at the foundation of living matter.  相似文献   

20.
Nanoparticles sized tens of nm with not only a highly complex but also a highly regular nanostructure, although ubiquitous in nature, are very difficult to prepare artificially. Herein, we report efficient solution‐based preparation of narrow‐disperse ABC three‐segment hierarchical nanoparticles (HNPs) with a size of tens of nm through a three‐level hierarchical self‐assembly of A‐b‐B‐b‐C triblock copolymers in solution. An ABC HNP is composed of three nanoparticles, A, B, and C that are linearly connected; in the ABC HNP, the B nanoparticle is sandwiched between the A and C nanoparticles. The method for the preparation is highly efficient, because all of the A‐b‐B‐b‐C chains in the solution are converted into the ABC HNPs. Furthermore, the ABC HNPs self‐assembled into Θ‐shaped HNPs tens nm in size. Both the ABC and Θ‐shaped HNPs, are highly complex but highly regular, and are novel HNPs, and they should be very promising for addressing various theoretical and practical problems.  相似文献   

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