Redox‐Active Hybrid Polyoxometalate‐Stabilised Gold Nanoparticles

We report the design and preparation of multifunctional hybrid nanomaterials through the stabilization of gold nanoparticles with thiol‐functionalised hybrid organic–inorganic polyoxometalates (POMs). The covalent attachment of the hybrid POM forms new nanocomposites that are stable at temperatures and pH values which destroy analogous electrostatically functionalised nanocomposites. Photoelectrochemical analysis revealed the unique photochemical and redox properties of these systems.     

Polystyrene‐Core–Silica‐Shell Hybrid Particles Containing Gold and Magnetic Nanoparticles

Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe₃O₄ nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors.     

金粒子包封介孔二氧化硅杂化载药控释体系

靶向给药控释体系既可以增强药物在病灶部位的疗效, 又可以降低药物对正常部位的毒副作用. 基于介孔二氧化硅为"容器"-金纳米粒子为"开关"(MSN-AuNPs)的杂化纳米阀门体系同时具备两种纳米粒子的优良特性, 在化学、生物材料以及临床医药等多学科受到广泛关注. 本文根据刺激手段和应用功能分类, 介绍了单一功能和多重功能的MSN-AuNPs杂化纳米阀门体系的重要研究进展, 以及目前面临的挑战和今后的发展方向.     

金纳米颗粒制备及应用研究进展

金纳米颗粒是近年研究的一种热门材料。介绍了金纳米颗粒主要的制备方法,包括化学还原法,两相法,晶种生长法以及模板法,并总结了金纳米粒子在生物医学、传感器、催化剂、电化学等领域的应用进展。     

Bioorthogonal Click of Colloidal Gold Nanoparticles to Antibodies In vivo

Combining nanotechnology and bioorthogonal chemistry for theranostic strategies offers the possibility to develop next generation nanomedicines. These materials are thought to increase therapeutic outcome and improve current cancer management. Due to their size, nanomedicines target tumors passively. Thus, they can be used for drug delivery purposes. Bioorthogonal chemistry allows for a pretargeting approach. Higher target-to-background drug accumulation ratios can be achieved. Pretargeting can also be used to induce internalization processes or trigger controlled drug release. Colloidal gold nanoparticles (AuNPs) have attracted widespread interest as drug delivery vectors within the last decades. Here, we demonstrate for the first time the possibility to successfully ligate AuNPs in vivo to pretargeted monoclonal antibodies. We believe that this possibility will facilitate the development of AuNPs for clinical use and ultimately, improve state-of-the-art patient care.     

Reversible Modulation of Surface Plasmons in Gold Nanoparticles Enabled by Surface Redox Chemistry

Switchable surface redox chemistry is demonstrated in gold@iron/iron oxide core–shell nanoparticles with ambient oxidation and plasmon‐mediated reduction to modulate the oxidation state of shell layers. The iron shell can be oxidized to iron oxide through ambient oxidation, leading to an enhancement and red‐shift of the gold surface plasmon resonance (SPR). This enhanced gold SPR can drive reduction of the iron oxide shell under broadband illumination to reversibly blue‐shift and significantly dampen gold SPR absorption. The observed phenomena provide a unique mechanism for controlling the plasmonic properties and surface chemistry of small metal nanoparticles.     

One‐Step Synthesis of Collagen Hybrid Gold Nanoparticles and Formation on Egyptian‐like Gold‐Plated Archaeological Ivory

A one‐step method is reported to synthesize hybrid gold nanoparticles (AuNPs) by reduction of HAuCl₄ in acetic solution in the presence of collagen (Col), dicarboxylic acid‐terminated polyethylene glycol (PEG), and cetyltetrammonium bromide (CTAB) mixed with hydoxyapatite (HAP) as surfactants. Such formation process of AuNPs was shown to be responsible for purple stains naturally formed on Egyptianizing archaeological gilded ivories from 8th BC Syria. The understanding of this formation mechanism, which most likely involves a step with hybrid AuNPs, allows the establishing of an authenticity marker of ancient gold‐plated ivories.     

Surface‐Passivated SBA‐15‐Supported Gold Nanoparticles: Highly Improved Catalytic Activity and Selectivity toward Hydrophobic Substrates

Silanol groups on a silica surface affect the activity of immobilized catalysts because they can influence the hydrophilicity/hydrophobicity, matter transfer, or even transition state in a catalytic reaction. Previously, these silanol groups have usually been passivated by using surface‐passivation reagents, such as alkoxysilanes, bis‐silylamine reagents, chlorosilanes, etc., and surface passivation has typically been found in mesoporous‐silicas‐supported molecular catalysts and heteroatomic catalysts. However, this property has rarely been reported in mesoporous‐silicas‐supported metal‐nanoparticle catalysts. Herein, we prepared an almost‐superhydrophobic SBA‐15‐supported gold‐nanoparticle catalyst by using surface passivation, in which the catalytic activity increased more than 14 times for the reduction of nitrobenzene compared with non‐passivated SBA‐15. In addition, this catalyst can selectively catalyze hydrophobic molecules under our experimental conditions, owing to its high (almost superhydrophobic) hydrophobic properties.     

Fluorescent Gold Nanoparticles: Synthesis of Composite Materials of Two‐Component Disulfide Gels and Gold Nanoparticles

Pseudoenantiomeric ethynylhelicene oligomers containing a disulfide group formed two‐component gels, which showed different solvent properties from gels without the disulfide group. The disulfide gels reacted with gold nanoparticles, and the resulting organic–inorganic composite materials exhibited fluorescence emission between 600–800 nm, along with emission from the oligomers at 450 nm. The disulfide gels and isolated gold nanoparticles loaded with the oligomers did not show the former emission. The 600–800 nm emission reversibly disappeared upon sol formation with heating, which was accompanied by an enhancement of the emission at 450 nm. The novel emission was also observed in the solid state.     

智能聚合物包覆的金纳米粒子*

本文综述了智能聚合物包覆的金纳米粒子的研究进展,重点介绍了智能聚合物包覆金纳米粒子的制备方法,包括原位合成法、配体置换法、表面引发聚合法和表面接枝聚合法等,以及智能聚合物包覆的金纳米粒子的智能响应类型,如温度敏感型、pH敏感型、pH/电解质双重敏感型、pH/温度双重敏感型、溶剂敏感型等。     

Photoactivated Nitrene Chemistry to Prepare Gold Nanoparticle Hybrids with Carbonaceous Materials

Photolysis of organic solvent soluble aryl azide‐modified gold nanoparticles (N₃‐AuNPs) with a core size of 4.6±1.6 nm results in the generation of interfacial reactive nitrene intermediates. The high reactivity of the nitrenes is utilized to tether the AuNP to the native surface of carbon nanotubes, and reduce graphene oxide and micro‐diamond powder, likely via addition to π‐conjugated carbon skeleton or insertion into the functionalities at the surface, to yield the desired hybrid material without the need for pretreatment of the surface. The AuNP‐covalent hybrid materials are robust in that they survive vigorous washing and sonication. In the absence of photolysis no attachment occurs with the same N₃‐AuNP. The nanohybrid AuNP‐nanohybrid materials are characterized using a combination of TEM, powder XRD, XPS and UV/Vis and IR spectroscopies. All of the characterization studies confirm the uniform incorporation of the AuNP on the irradiated substrates.     

In Situ Formation of Dual‐Phase Thermosensitive Ultrasmall Gold Nanoparticles

A novel method for the in situ synthesis of dual‐phase thermosensitive ultrasmall gold nanoparticles (USGNPs) with diameters in the range of 1–3 nm was developed by using poly(N‐isopropylacrylamide)‐block‐poly(N‐phenylethylenediamine methacrylamide) (PNIPAM‐b‐PNPEDMA) amphiphilic diblock copolymers as ligands. The PNPEDMA block promotes the in situ reduction of gold precursors to zero‐valent gold and subsequently binds to the surface of gold nanoparticles, while PNIPAM acts as a stabilizing and thermosensitive block. The as‐synthesized USGNPs stabilized by a thermosensitive PNIPAM layer exhibit a sharp, reversible, clear–opaque transition in aqueous solution between 30 and 38 °C. An unprecedented finding is that these USGNPs also show a reversible soluble–precipitate transition in nonpolar organic solvents such as chloroform at around 0 °C under acidic conditions.     

Calix[4]arene‐Functionalised Silver Nanoparticles as Hosts for Pyridinium‐Loaded Gold Nanoparticles as Guests

A series of lipophilic gold nanoparticles (AuNPs) circa 5 nm in diameter and having a mixed organic layer consisting of 1‐dodecanethiol and 1‐(11‐mercaptoundecyl) pyridinium bromide was synthesised by reacting tetraoctylammonium bromide stabilised AuNPs in toluene with different mixtures of the two thiolate ligands. A bidentate ω‐alkylthiolate calix[4]arene derivative was instead used as a functional protecting layer on AgNPs of approximately 3 nm. The functionalised nanoparticles were characterised by transmission electron microscopy (TEM), and by UV/Vis and X‐ray photoelectron spectroscopy (XPS). Recognition of the pyridinium moieties loaded on the AuNPs by the calix[4]arene units immobilised on the AgNPs was demonstrated in solution of weakly polar solvents by UV/Vis titrations and DLS measurements. The extent of Au‐AgNPs aggregation, shown through the low‐energy shift of their surface plasmon bands (SPB), was strongly dependent on the loading of the pyridinium moieties present in the organic layer of the AuNPs. Extensive aggregation between dodecanethiol‐capped AuNPs and the Ag calix[4]arene‐functionalised NPs was also promoted by the action of a simple N‐octyl pyridinium difunctional supramolecular linker. This linker can interdigitate through its long fatty tail in the organic layer of the dodecanethiol‐capped AuNPs, and simultaneously interact through its pyridinium moiety with the calix[4]arene units at the surface of the modified AgNPs.     

Assembly of Gold Nanoparticles on Functionalized Si(100) Surfaces through Pseudorotaxane Formation

The assembly of gold nanoparticles (AuNPs) on a hydrogenated Si(100) surface, mediated by a series of hierarchical and reversible complexation processes, is reported. The proposed multi‐step sequence involves a redox‐active ditopic guest and suitable calix[n]arene‐based hosts, used as functional organic monolayers of the two inorganic components. Surface reactions and controlled release of AuNPs have been monitored by application of XPS, atomic force microscopy (AFM), field‐emission scanning electron microscopy (FESEM) and electrochemistry.     

Controlling the Surface Functionalization of Ultrasmall Gold Nanoparticles by Sequence-Defined Macromolecules

Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by ¹H NMR spectroscopy, ¹H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative ¹H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm² per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles.