纳米粒子的界面自组装

近年来,随着纳米技术的发展及Pickering乳液在食品、化妆品、医药等领域中的应用,纳米粒子的界面自组装现象引起了人们的广泛关注。界面能的降低是纳米粒子液液界面自组装的主要驱动力。通过改变纳米粒子的尺寸和表面配体的化学性质,可控制纳米粒子的界面自组装行为。本文综述了不同类型纳米粒子实现界面自组装的研究工作,包括均质纳米粒子、Janus纳米粒子、棒状纳米粒子以及生物纳米粒子。最后,对纳米粒子的界面组装这一领域的可能发展做了展望。     

纳米粒子组装体系的研究进展

制备纳米粒子组装体系是构筑纳米结构的重要方法之一，本文综述了纳米粒子组装体系的制备方法及其性质和应用研究。     

纳米粒子的控制生长和自组装研究进展

由于在纳米器件上潜在应用,通过化学方法控制的纳米粒子生长,以及纳米粒子自组装的一维、二维和三维点阵受到人们的广泛关注。本文介绍来近年来纳米粒子的控制生长和组装研究的现状。主要探讨了有机稳定剂对纳米粒子形状和尺寸控制的影响。含配位基团和长链烷烃的有机化合物不但可以用控制纳米粒子生长的稳定剂,而且可以用作纳米粒子自组装的模板剂。     

纳米粒子的程序化自组装研究进展

纳米粒子的自组装作为自下而上构筑纳米组装结构的简便且高效的策略而受到广泛关注,但在组装结构的精准性、多样性以及可操控性等方面仍面临较大的挑战.纳米粒子的程序化自组装是指特定的纳米粒子基元按照预先编好的程序自发排列成位置和取向等空间排列方式受到精准调控的组装结构,其更强调任意构筑一系列符合预先设定结构的多种形式纳米粒子组装体.本文总结了应用于纳米粒子程序化自组装的四类常用策略,即类原子成键、区域选择性修饰、模板引导和物理场调控,着重评述了近年来该领域的一些重要进展,并对纳米粒子程序化自组装的未来发展做了展望.     

嵌段共聚物调控纳米粒子自组装的研究进展

嵌段共聚物和纳米粒子复合纳米材料具有优异的性能,在生物医药、光电材料、催化材料等领域具有很大的应用价值,已成为备受关注的研究热点.利用嵌段共聚物自组装能够形成特定形态的纳米结构聚集体,将纳米粒子选择性的分布和定位于嵌段共聚物聚集体中,可以改善纳米粒子的性能及其应用.本文综述了近年来实验上利用自组装制备嵌段共聚物-纳米粒子复合纳米材料的方法,并总结分析了影响纳米粒子在嵌段共聚物聚集体中的分布和定位的各种因素,包括纳米粒子的大小、形状及其表面化学.最后总结了嵌段共聚物-纳米粒子的自组装在理论模拟方面的研究.     

原位自组装形成二氧化硅/十六烷基三甲基溴化铵纳米网络粒子

提出了以具有纳米尺寸孔径及孔壁厚度的MCM 48作为无机基体、以无机 有机原位自组装的方法形成纳米网络粒子 .研究结果表明 ,在一定实验条件下 ,有机相可进入无机相的三维孔道自组装形成立方有序结构的纳米网络复合粒子 .通过研究纳米网络粒子在极性介质和非极性介质中的分散发现 ,有机相的存在有利于纳米网络粒子的分散     

聚苯胺纳米粒子的反胶束法合成及自组装

聚苯胺纳米粒子的反胶束法合成及自组装;聚苯胺;纳米粒子;反胶束;自组装     

Papain/HA-Phe自组装复合纳米粒子及乳化性能

用L-苯丙氨酸乙酯(L-Phe)改性透明质酸(HA)双亲性生物大分子(HA-Phe)负载生物活性分子木瓜蛋白酶(papain),HA-Phe和Papain通过静电、氢键和疏水相互作用自组装形成生物基Papain/HA-Phe复合纳米粒子.用动态光散射(DLS)和透射电镜(TEM)对复合纳米粒子的尺寸和形貌进行表征.结果显示,形成的复合纳米粒子为球形结构,粒径约308 nm.以此复合纳米粒子为颗粒乳化剂稳定白油,形成水包油型Pickering乳液.乳液的扫描电镜(SEM)显示,复合纳米粒子吸附在油水界面,形成复合纳米粒子的吸附层以稳定乳液.详细研究了pH和盐浓度对复合纳米粒子性质和复合纳米粒子乳化性能的影响.结果表明,随着pH增加,复合纳米粒子在油滴表面的吸附数目减少,乳化性能降低;随着盐浓度增加,复合纳米粒子的形变能力增强,乳化性能提高.进一步研究了乳液中木瓜蛋白酶的活性及美白效果.研究表明,制备的乳液保留了一定的活性,且具有一定的美白效果.     

有机大分子导向无机纳米粒子的分级有序自组装

本文主要综述了基于特定分子设计的有机大分子导向下的无机纳米粒子的分级有序自组装.可以有效导向无机纳米粒子组织的有机大分子主要包括合成大分子和生物大分子,前者如具有氢键识别功能的大分子、聚电解质、嵌段大分子、树枝状大分子;后者如DNA、糖类以及蛋白质.所涉及的无机纳米粒子通常需要通过单层修饰使之与特定的大分子具有识别功能,或者设计表面带有正或负电荷使之与带有负或正电荷的大分子相互识别.该领域的研究在先进功能材料及仿生材料方面具有重要意义.     

聚合物/无机纳米粒子自组装复合膜的制备与应用

对聚合物/无机纳米粒子二维自组装复合膜的制备方法进行了系统地分类阐述,在详细介绍各种方法的特点的基础上比较了它们各自的优缺点.并简述了这类复合膜在应用方面的最新研究成果.     

Controlled Self-Assembly of Metallacycle-Bridged Gold Nanoparticles for Surface-Enhanced Raman Scattering

In this work, well-defined two-dimensional metallacycles have been successfully employed for the well-controlled self-assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water–oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well-defined system for studying the hot-spot phenomenon in surface-enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing.     

基于纳米材料自组装的传感器在生化分析中的应用研究进展

纳米材料可以通过自组装技术可控地形成具有不同空间结构的材料,该技术使其及其自组装体在多种生化物质（如蛋白质、多肽、DNA等）和金属离子的超灵敏检测中具有重要应用。本文对基于半导体量子点、贵金属纳米材料和碳基纳米材料自组装体系的传感器在生化分析中的应用进行了总结。     

Reversible Self-Assembly of Gold Nanoparticles Based on Co-Functionalization with Zwitterionic and Cationic Binding Motifs**

We report a pH- and temperature-controlled reversible self-assembly of Au-nanoparticles (AuNPs) in water, based on their surface modification with cationic guanidiniocarbonyl pyrrole (GCP) and zwitterionic guanidiniocarbonyl pyrrole carboxylate (GCPZ) binding motifs. When both binding motifs are installed in a carefully balanced ratio, the resulting functionalized AuNPs self-assemble at pH 1, pH 7 and pH 13, whereas they disassemble at pH 3 and pH 11. Further disassembly can be achieved at elevated temperatures at pH 1 and pH 13. Thus, we were able to prepare functionalized nanoparticles that can be assembled/disassembled in seven alternating regimes, simply controlled by pH and temperature.     

Selectivity in the Ligand Functionalization of Photocatalytic Metal Oxide Nanoparticles for Phase Transfer and Self-Assembly Applications

The functionalization of photocatalytic metal oxide nanoparticles of TiO₂, ZnO, WO₃ and CuO with amine-terminated (oleylamine) and thiol-terminated (dodecane-1-thiol) alkyl-chain ligands was studied under ambient conditions. A high selectivity was observed in the binding specificity of a ligand towards nanoparticles of these different oxides. It was observed that oleylamine binds stably to only TiO₂ and WO₃, whereas dodecane-1-thiol binds stably only to ZnO and CuO. Similarly, polar-to-nonpolar solvent phase transfer of TiO₂ and WO₃ nanoparticles could be achieved by using oleylamine, but not dodecane-1-thiol, whereas the opposite holds for ZnO and CuO. The surface chemistry of ligand-functionalized nanoparticles was probed by attenuated total reflectance (ATR)-FTIR spectroscopy, which enabled the occupation of the ligands at the active sites to be elucidated. The photostability of the ligands on the nanoparticle surface was determined by the photocatalytic self-cleaning properties of the material. Although TiO₂ and WO₃ degrade the ligands within 24 h under both UV and visible light, ligands on ZnO and CuO remain unaffected. The gathered insights are also highly relevant from an application point of view. As an example, because the ligand-functionalized nanoparticles are hydrophobic in nature, they can be self-assembled at the air-water interface to give nanoparticle films with demonstrated photocatalytic as well as anti-fogging properties.     

LbL层层纳米自组装法制备新型微胶囊*

本文介绍了一种新颖、灵活的制备纳米或微米胶囊方法--层层纳米自组装法(LbL)。LbL法制备微胶囊的显著优越性在于能够在纳米尺度上对胶囊的大小、组成、结构、形态和囊壁厚度进行精确的控制.这种新型的微胶囊在生化、制药、药物控释、化妆品和催化等领域具有潜在的应用前景。     

Polymersome-Embedded Nanoparticles

Summary: Polymersomes are self assembled vesicles composed of fully synthetic amphiphilic diblock copolymers. Many of their properties are similar to lipid vesicles, although with often higher thermal and mechanical stability within their curved membrane. Incorporation of nanosized objects into their hydrophilic interior or hydrophobic membrane represents an important method for functionalization of these biomimetic structures. We report on the embedding of hydrophobic gold nanoparticles (Au-NPs) into polymersomes. Nanoparticles were prepared and incorporated into polymersomes made by standard film rehydration techniques from commercially available diblock copolymers. Characterization of the resulting structures was achieved by dynamic light scattering (DLS) and by TEM. Results on the preparation method, its influence on the polymersome stability and the application of these new membrane-mimetics are reported.     

Self-Assembly and Aggregation-Induced Emission in Aqueous Media of Responsive Luminescent Copper(I) Coordination Polymer Nanoparticles

Luminescent copper(I)-based compounds have recently attracted much attention since they can reach very high emission quantum yields. Interestingly, Cu(I) clusters can also be emissive, and the extension from small molecules to larger architecture could represent the first step towards novel materials that could be obtained by programming the units to undergo self-assembly. However, for Cu(I) compounds the formation of supramolecular systems is challenging due to the coordinative diversity of copper centers. This works shows that this diversity can be exploited in the construction of responsive systems. In detail, the changes in the emissive profile of different aggregates formed in water by phosphine-thioether copper(I) derivatives were followed. Our results demonstrate that the self-assembly and disassembly of Cu(I)-based coordination polymeric nanoparticles (CPNs) is sensitive to solvent composition. The solvent-induced changes are related to modifications in the coordination sphere of copper at the molecular level, which alters not only the emission profile but also the morphology of the aggregates. Our findings are expected to inspire the construction of smart supramolecular systems based on dynamic coordinative metal centers.