Gold Nanoparticles Thin Films with Thermo‐ and Photoresponsive Plasmonic Properties Realized with Liquid‐Crystalline Ligands

Robust synthesis of large‐scale self‐assembled nanostructures with long‐range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV‐light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long‐range ordered structures which exhibit a novel dual‐responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV‐light irradiation. These results present an efficient way to obtain bulk quantities of self‐assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix‐assisted or DNA‐mediated organization.     

真空镀膜法制备纳米铝颗粒膜及其表面等离激元共振特性研究

采用直流磁控溅射镀膜技术制备了纳米铝颗粒膜,并尝试通过两种方式获得纳米铝的表面等离激元共振吸收峰,一种是先在室温石英基底上沉积纳米铝,再进行真空退火;另一种是在热石英基底上沉积纳米铝。用透射电镜和扫描电子显微镜、X-射线光电子谱、紫外-可见吸收光谱表征了样品的形貌和晶态结构、成份和吸收特性。采用比对的方式,研究了基底温度、沉积时间对两种方法制备的纳米铝表面等离激元共振的影响。结果表明,先沉积纳米铝,再进行真空退火,不能获得表面等离激元共振吸收峰,而在热基底上沉积纳米铝,可以获得明显的表面等离激元共振吸收峰。通过调控沉积时间和沉积温度实现了纳米铝表面等离激元共振峰从紫外光区到可见光区的可控移动。而且,研究发现对于平均厚度大于3 nm的纳米铝薄膜,由于纳米铝氧化具有自限性,其表面等离激元共振特性在空气中稳定且主要取决于纳米铝颗粒的团聚度。本研究对理解纳米铝表面等离激元共振特性及其应用具有指导意义。     

Plasmon Resonance Energy Transfer: Coupling between Chromophore Molecules and Metallic Nanoparticles

Plasmon resonance energy transfer (PRET) from a single metallic nanoparticle to the molecules adsorbed on its surface has attracted more and more attentions in recent years. Here, a molecular beacon (MB)‐regulated PRET coupling system composed of gold nanoparticles (GNPs) and chromophore molecules has been designed to study the influence of PRET effect on the scattering spectra of GNPs. In this system, the chromophore molecules are tagged to the 5′‐end of MB, which can form a hairpin structure and modified on the surface of GNPs by its thiol‐labeled 3′‐end. Therefore, the distance between GNPs and chromophore molecules can be adjusted through the open and close of the MB loop. From the peak shift, the PRET interactions of different GNPs‐chromophore molecules coupling pairs have been calculated by discrete dipole approximation and the fitting results match well with the experimental data. Therefore, the proposed system has been successfully applied for the analysis of PRET situation between various metallic nanoparticles and chromophore molecules, and provides a useful tool for the potential application in screening the PRET‐based nanoplasmonic sensors.     

DNA‐Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self‐assembly strategy through a one‐step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size‐ and distance‐dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near‐field plasmonic properties.     

Electrospinning Nanofibers as Uniaxially Aligned Arrays and Layer‐by‐Layer Stacked Films

The conventional procedure for electrospinning has been modified to generate nanofibers as uniaxially aligned arrays over large areas. The key to the success of this method was the use of a collector composed of two conductive strips separated by an insulating gap of variable width. Directed by electrostatic interactions, the charged nanofibers were stretched to span across the gap and became uniaxially aligned arrays. Two types of gaps have been demonstrated: void gaps and gaps made of a highly insulating material. When a void gap was used, the nanofibers could readily be transferred onto the surfaces of other substrates for various applications. When an insulating substrate was involved, the electrodes could be patterned in various designs on the solid insulator. In both cases, the nanofibers could be conveniently stacked into multi‐layered architectures with controllable hierarchical structures. This new version of electrospinning has already been successfully applied to a range of different materials that include organic polymers, carbon, ceramics, and composites.