Selfassembly of Metallic Nanoparticle Arrays by DNA Scaffolding

We report the self-assembly of metallic nanoparticle arrays using DNA crystals as a programmable molecular scaffolding. Gold nanoparticles, 1.4nm in diameter, are assembled in two-dimensional arrays with interparticle spacings of 4 and 64nm. The nanoparticles form precisely integrated components, which are covalently bonded to the DNA scaffolding. These results show that heterologous chemical systems can be assembled into precise, programmable geometrical arrangements by DNA scaffolding, thereby representing a critical step toward the realization of DNA nanotechnology.     

Order and Defects in Ceramic Semiconductor Nanoparticle Superstructures as a Function of Polydispersity and Aspect Ratio

The supreme aim of nanoparticle‐based materials is to achieve new properties extending over the features of individual constituents. The emergence of cooperativity necessitates precise positioning and orientation of nanoparticle ensembles. Thus, it is important to understand and learn how to control self‐assembly processes of nanoparticles. Besides shape, the structural uniformity plays a key role for ordering in superstructures. Therefore, it is challenging to synthesize nanorods with narrow polydispersity. An analysis of the systematic variation of aspect ratio and polydispersity is missing. A series of zinc oxide nanorods is presented and it is shown that their formation resembles step‐polymerization with an amorphous precursor state as a monomer and polar ZnO particles as entities capable of growing. The width of nanorods is kept constant (15 nm) and the length is varied between 20 and 100 nm, as well as improving the polydispersity of the nanorod length from 36% to 10%. Best samples have been achieved by post‐preparative treatment using gradient centrifugation. A method has been developed for semiquantitative evaluation of orientational order. Ordering in structures formed by quasispherical particles is always low despite low polydispersity. For rod‐like nanoparticles with increasing aspect ratio, superstructure order depends on the occurrence of different defects, which correlate differently to nanoparticle polydispersity.     

Molecular Self‐Assembly of Multifunctional Nanoparticle Composites with Arbitrary Shapes and Functions: Challenges and Strategies

The assembly of nanoparticles into complicated, anisotropic shapes has much promise for advanced materials and devices. Developing effective and efficient anisotropic mono‐functionalization strategies is an imperative step in realizing this potential. By functionalizing DNA one at a time to the nanoparticle, a DNA‐nanoparticle building block could have distinct DNA sequences at different locations on the surface of the particle. Since this technology could incorporate nanoparticles of different composition, generating toolboxes of various nanoparticle building blocks (“nano‐toolboxes”) with DNA at defined locations and in defined 3D orientations on a nanoparticle, it promises not only complicated shapes, but also the ability to tune the function of the assembly. The challenges of programmable and scalable multifunctional nanostructure self‐assembly with DNA conjugated to nanoparticles are reviewed. The first difficulty is to control the assembly process so that designed products are formed, and unwanted products are minimized. The design problem for nanostructure construction is both physically and computationally complex. Thus, the other major challenge is to devise design methodologies that move nanostructure construction from trial and error to principled approaches. Strategies to overcome these challenges are also presented by realizing greater control over the final shapes and functions of the self‐assembled nanostructures. Finally, the future perspectives of nano‐toolboxes and their promise in applications such as multifunctional, multicolor, and multimodal contrast nanoagents for medical therapy and diagnostics (theranostics) are described.     

Controlled Self‐Assembly of Mesoporous CuO Networks Guided by Organic Interlinking

The controlled aggregation of copper oxide nanoparticles (CuO NPs) induced by a multitopic carboxylic acid allows the formation of mesoporous structures with high surface area, in the order of 100 m² g^?1, as demonstrated herein. The main novelty in the designed process is the use, as a previous step, of a sacrificeable monotopic carboxylate ligand for capping the CuO NPs. This step avoids the often observed unwanted behavior of uncontrolled aggregation and material densification. The monotopic 3,6,9‐trioxadecanoate (HTODA) is used as the capping agent to prepare TODA@CuO, a starting material that forms colloidal dispersions in ethanol. For NPs self‐assembly, the bulky tricarboxylic acid 4,4′,4′′,‐benzene‐1,3,5‐triyl‐tris(benzoic acid) (H₃BTB) is chosen as an efficient interlinker in the controlled aggregation. The obtained mesoporous network shows a considerable thermal stability, retaining ≈70% of its specific surface area after annealing at 300 °C under vacuum. Thermal treatment involves TODA capping agent elimination, but not BTB linker. The simultaneous reduction of the CuO NPs to a Cu₂O/Cu mixture is observed.     

Destabilization of Thiolated Gold Clusters for the Growth of Single‐Crystalline Gold Nanoparticles and Their Self‐Assembly for SERS Detection

Thiolate‐protected gold nanoclusters with high chemical stability are exploited extensively for fundamental research and utility in chosen applications. Here for the first time, the controlled destabilization of extraordinarily stable thiolated gold clusters for the growth of single‐crystalline gold nanoparticles (AuNPs) is demonstrated, which was achieved simply via the oxidation of surface‐protecting thiolates into disulfides by hydrogen peroxide under basic condition. By combining with our experimental observations over the entire destabilization and growth process, the new growth mechanism from clusters to AuNPs is revealed by density functional theory (DFT) calculations. It is found that the size of AuNPs decreases with the increase of hydrogen peroxide concentration due to the generation of more nuclei at the higher hydrogen peroxide concentrations. In addition, the preparation of AuNPs is tuned by changing the concentration of hydrogen peroxide, and they are self‐assembled into microspheres via an evaporation‐mediated process, which can induce strong plasmonic coupling between adjacent AuNPs for ultrasensitive surface‐enhanced Raman scattering detection. The present work demonstrates a facile route to functionalize and engineer AuNPs via controlling the reaction conditions and the ratio of precursors, and thus bring new possibilities for using more clusters as precursors to construct novel nano/microstructures for various applications.     

An Improved Method for Site‐Specific End Modification of Zeolite L for the Formation of Zeolite L and Gold Nanoparticle Self‐Assembled Structures

The ability to site‐selectively modify micro‐ and nanosized particles has allowed for directed self‐assembly in two and three dimensions. Site‐selective modification of particles can be a complicated task requiring the pre‐organization of particles or enhanced particle fabrication methods. The aluminum silicate, zeolite L has been reported to undergo site‐specific modification at the zeolite channel entrances, post‐fabrication in a solution‐based method. The process by which the channel entrances are site selectively modified is explored here. The preliminary step of charging the zeolite channels with aqueous acid allows for catalysis of covalent bond formation at the channel entrances. Three new end‐specific modification reagents are described based on silanol and silyl ether functional groups. These reagents are purified by column chromatography and characterized by¹H NMR spectroscopy and high resolution mass spectrometry (HRMS); they provide for reliable end modification of zeolites L. Preferential reactivity at the channel entrances is also observed. The utility of the approach is demonstrated by modifying zeolite L with adamantane at the channel entrances. Site‐specific self‐assembly with β‐cyclodextrin coated gold nanoparticles can be triggered with a chemical stimulus. The resulting multivalent host‐guest interactions give gold clustered nanoparticles at the ends of the micrometer‐sized zeolites.     

Microwell‐Directed Self‐Assembly of Vertical Nanowire Arrays

Vertical arrays of anisotropic particles are desired for many applications including solar cells, battery electrodes, and lasers. Partially etched nano­wires (PENs) are hybrid silica nanotube/nanowires with partial metallic cores. These particles spontaneously form vertical arrays in which on average 70% of the particles are oriented perpendicular to the underlying substrate. Here, we perform PEN self‐assembly on lithographically prepared substrates patterned with square microwells having dimensions comparable to the length of the particles. Particle self‐assembly is observed both in the microwells and on the intervening surfaces. PENs both directly deposit into a well and diffuse across the surface between microwells until falling into a well. Assembly occurs as the local concentration of PENs in a well increases by these two mechanisms. Microwells provide a way to control array location on a surface and improve standing percentages up to 100% when the edge dimensions are decreased to a size approximately equal to the nanowire length. Micro­wells also protect against array disruption during sample drying.     

Colloidal Nanoparticles: Formation of Large 2D Arrays of Shape‐Controlled Colloidal Nanoparticles at Variable Interparticle Distances (Part. Part. Syst. Charact. 1/2013)

A method for the production of homogeneous layers of nanoparticles of arbitrary shape is presented. The method relies on a ligand exchange with a functionalized polymer and a subsequent self‐assembly of a thin film on the substrates. The interparticle distances in the layer can be adjusted by the length of the polymer. In the case of spherical particles, the approach yields quasi‐hexagonal structures; in the case of anisotropic particles, the minimum distance between adjacent particles is controlled. Regular arrangements of the nanoparticles covering areas of several square centimeters are achieved.     

Experimental Study of a Nanoparticle Virtual Impactor

A nanoparticle virtual impactor was constructed and its performance under different operating conditions was investigated. Experimental evaluations showed that the nanoparticle virtual impactor has a 50% cutoff size ranging from 15 to 60nm. Further, the cutoff size of 60nm can be achieved at an impactor chamber pressure of 220torr when the nozzle upstream pressure is 760torr. This pressure level is much higher than that of thin-plate orifice nozzle impactors, which require 12torr to achieve the cutoff size of 66nm. Thus, the proposed virtual impactor can be operated with a small vacuum pump, which is more preferable for practical applications.In this study, the effects of design parameters on the impactor performance have also been experimentally investigated. The parameters include the separation distance between the collection probe and the acceleration nozzle, the pressure ratio of the upstream and downstream chambers, the diameter ratio of the collection probe and the nozzle, the flow ratio of the minor and total flows, total mass flow rates and the upstream pressure. The experimental data obtained were then scaled with the Stokes number defined by previous researchers. The performance of the proposed nanoparticle virtual impactors can therefore be estimated when the operating variables are given or measured. An important finding in this parametric study is that the optimal diameter ratio of collection probe to nozzle is around 1.8. It is different from the value of 1.4 recommended in previous studies with virtual impactors for submicron particle applications.     

金纳米粒子的图案化组装及表面增强拉曼光谱研究

利用聚苯乙烯纳米粒子有序组装结构为模板,进行了金纳米粒子的图案化组装。金纳米粒子在聚苯乙烯纳米粒子底部自组装聚集,形成规则的“面包圈”结构。表面增强拉曼光谱表明,相对于随机分布的金纳米粒子而言,金纳米粒子组装结构具有聚焦电磁场作用,从而使吸附的对巯基苯甲酸的拉曼散射得以进一步增强。     

Deliberate Introduction of Particle Anisotropy in Helical Gold Nanoparticle Superstructures

Helical nanoparticle (NP) superstructures are an important class of chiral NP assemblies. The nature of the constituent NPs (size and shape) within these assemblies dictates their optical properties. However, the construction of helical NP superstructures consisting of various anisotropic NPs remains challenging. Here, a set of cetyltrimethylammonium bromide derivatives is employed to transform constituent spherical gold NPs (≈3 nm) within a chiral single‐helical assembly into gold nanoprisms (edge length ? 10 nm). Careful optimization of this strategy may lead to designed chiral NP architectures with tunable optical properties.     

碳纳米粒子悬浮液光限幅性能数值模拟

碳纳米粒子悬浮液具有良好的光限幅性质,是一种优良的宽波段光限幅材料。通过热传导方程和米氏散射理论建立了微气泡半径与入射光能量、碳纳米粒子悬浮液散射系数和透过率的理论模型。采用Matlab数值模拟了散射系数随微气泡尺寸因子的变化关系,碳纳米粒子悬浮液光限幅性能随入射光能量的变化规律。研究了气泡尺寸因子、入射激光能量以及波长对碳纳米粒子悬浮液光限幅特性的影响。研究发现当激光能量达到一定值时,微气泡的半径保持恒定,不再随入射激光能量的增加而增加。微气泡尺寸的增大对碳纳米粒子悬浮液的透过率有着显著的影响。同时,碳纳米粒子悬浮液对不同入射光波长和光能表现出不同的光限幅性能。研究结果为实验研究提供了理论指导。     

Survey of Plasmonic Nanoparticles: From Synthesis to Application

The unique properties of plasmonic nanostructures have fuelled research based on the tremendous amount of potential applications. Their tailor‐made assemblies in combination with the tunable size and morphology of the initial building blocks allow for the creation of materials with a desired optical response. In this respect, it is crucial to synthesize nanoparticles with a defined shape that are at the core of such developments. Moreover, the interaction of individual nanoparticles with an incident electromagnetic field cannot only be influenced by their structure, but in fact, also by their spatial arrangement to each other. To harvest such opportunities, a profound theoretical understanding of these interactions is required as well as concise strategies to create such ordered assemblies. A quantitative evaluation of their optical properties can only be conducted when discrete structures of high uniformity can be achieved. As a consequence, separation steps have to be applied in order to obtain materials of high purity and uniformity. This also allows for an easier structural characterization of the nanoparticles and their assembled superstructures. In this progress report, an overview about the current development in this field of research is provided.     

Self‐Assembly of Ag6 Clusters into Nanowires for Nonenzymatic Electrochemical Sensing of Glucose

Self‐assembly of metal nanoclusters into 3D ordered superstructures and the exploration of their electrochemical properties are highly significant for fundamental research and practical application. In this study, atomically precise Ag₆(NALC)₅ nanoclusters are successfully synthesized and their structure is determined carefully. It is interesting that the prepared Ag₆(NALC)₅ nanoclusters can be self‐assembled into ultrafine nanowires, long ribbons, and finally 3D porous network in the mixed solution of water and ethanol, which can be attributed to the solvent polarity, static electricity interaction between ligands, and the possible Van der Waals attractions. Such assembly phenomenon lays a foundation for the future fabrication of silver clusters‐based nanodevices. In addition, the synthesized silver nanoclusters can be used for electrochemical sensing of glucose with high detection sensitivity, selectivity, and low limit of detection. This work is expected to be helpful for the synthesis of atomically precise metal nanoclusters and their applications in fabrication of nanodevices for chemical sensors.